JP5266131B2 - Optical three-dimensional resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition for optical stereolithography, which gives an optically shaped article that has a high photocoagulation sensibility, a low viscosity, an excellent handling characteristic in shaping, a high resolution, a low volume shrinkage rate in hardening, a high heat distortion temperature, an excellent heat resistance, a high mechanical strength, and an excellent toughness, and is further also excellent in transparency and hue. <P>SOLUTION: The resin composition for optical stereolithography includes a cation-polymerizable organic compound, a radical polymerizable organic compound, a cation polymerization initiator, and a radical polymerization initiator, in which 5-50 mass% of triepoxy compound represented by formula (A-1) is contained as the cation-polymerizable organic compound. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

  The present invention has a high heat distortion temperature, excellent heat resistance, large tensile strength and bending strength, excellent mechanical strength, moderate elongation, excellent toughness, and further transparency. Excellent optical discoloration such as yellowing and small hue, excellent hue, and smoothness with high light-curing speed and high modeling accuracy for the above-mentioned optical three-dimensional object that maintains excellent transparency and hue even when exposed to high temperatures. Furthermore, the present invention relates to a resin composition for optical three-dimensional modeling that can be manufactured with high productivity and a method for manufacturing an optical three-dimensional model using the resin composition for optical three-dimensional modeling.

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.

The resin or resin composition used for optical three-dimensional modeling has high curing sensitivity by active energy rays and can produce a three-dimensional model in a short modeling time, has low viscosity and excellent handling at the time of modeling, In addition, there is a need that the absorption of moisture and moisture is small and the curing sensitivity is not lowered, that the resolution of the modeled object is high and that the modeling accuracy is excellent, and that the volumetric shrinkage rate during curing is small. In addition, in recent years, optical three-dimensional objects have been used at high temperatures or under conditions where external force is applied, and accordingly, the heat distortion temperature is high, heat resistance is excellent, and mechanical There has been a demand for a resin composition for optical three-dimensional modeling that is capable of producing a three-dimensional model that has high strength and toughness, is not easily damaged, and has excellent durability.
However, the improvement in toughness in the optical three-dimensional object and the improvement in heat distortion temperature are usually in a trade-off relationship, and if one tries to improve the toughness by increasing the flexibility of the three-dimensional object, the heat deformation of the three-dimensional object Generally, the temperature decreases and the heat resistance decreases.
Furthermore, depending on the application of the optical three-dimensional object, etc., an optical solid that has excellent transparency, little discoloration such as yellowing, excellent hue, and maintains excellent transparency and hue even when exposed to high temperatures. There is a strong demand for a resin composition for optical three-dimensional modeling that gives a modeled object.

Conventionally, as a resin composition for optical three-dimensional modeling, an acrylate-based photocurable resin composition, a urethane acrylate-based photocurable resin composition, an epoxy-based photocurable resin composition, and an epoxyacrylate-based photocurable resin composition And vinyl ether photocurable resin compositions have been proposed and used. Among these, the epoxy-based photocurable resin composition can form a molded article having excellent dimensional accuracy.
However, it has been pointed out that an epoxy-based photocurable resin composition proceeds with cations generated by light irradiation, so that the reaction rate is slow and it takes too much time for modeling.
Therefore, for the purpose of shortening the modeling time by improving the reaction rate, an optical three-dimensional modeling resin composition containing a radical polymerizable organic compound together with a cationically polymerizable organic compound such as an epoxy compound has been used ( For example, patent documents 1, 2 and many other)

However, a three-dimensional model obtained from a conventional resin composition for optical three-dimensional modeling as described in Patent Documents 1 and 2, which contains a cationic polymerizable organic compound and a radical polymerizable organic compound, It cannot be said that the heat distortion temperature is low and heat resistance is sufficient, and it is not fully satisfactory in terms of mechanical strength, toughness, etc., and transparency is greatly reduced when exposed to higher temperatures. Or discoloration such as yellowing is often significant.
In particular, the technique of Patent Document 2 aims to obtain an opaque optical three-dimensional object from the resin composition for optical three-dimensional object, and does not meet the demand for obtaining a transparent three-dimensional object. Met.

JP 2007-23250 A JP 2007-2073 A

The purpose 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 irradiation time of active energy rays, low viscosity and excellent handling properties at the time of modeling, It has excellent properties such as high resolution of objects, excellent molding accuracy, and low volumetric shrinkage during curing, high heat distortion temperature, excellent heat resistance, and excellent mechanical strength and toughness. For optical three-dimensional modeling that can produce a three-dimensional model that has superior transparency, small discoloration such as yellowing and excellent hue, and maintains the excellent transparency and hue even when exposed to high temperatures It is to provide a resin composition.
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 problems, the present inventors have repeatedly studied. As a result, the present inventors in a resin composition for optical three-dimensional modeling containing a cationically polymerizable organic compound, a radically polymerizable organic compound, an active energy ray sensitive cationic polymerization initiator and an active energy ray sensitive radical polymerization initiator When a specific aromatic triepoxy compound is contained as a cationic polymerizable organic compound in a predetermined ratio, the three-dimensional structure obtained from the optical three-dimensional resin composition has a high heat distortion temperature and is heat resistant. Excellent mechanical strength such as tensile strength and flexural strength and has a moderate elongation, excellent toughness, excellent transparency, small discoloration such as yellowing, excellent hue, excellent It has been found that transparency and hue are maintained even after exposure to high temperatures.

  Furthermore, the present inventors contain a cationically polymerizable organic compound, a radically polymerizable organic compound, an active energy ray-sensitive cationic polymerization initiator and an active energy ray-sensitive radical polymerization initiator, and further specified as a cationically polymerizable organic compound. When the above-mentioned resin composition for optical three-dimensional modeling containing an aromatic triepoxy compound further contains nano-silica particles having a nano-sized average particle diameter in a predetermined ratio, good mechanical properties and excellent transparency It has been found that an optical three-dimensional object having a higher heat distortion temperature and further excellent heat resistance can be obtained while maintaining an excellent hue with little discoloration such as property and yellowing.

  Further, the present inventors include, in the optical three-dimensional modeling resin composition, at least one kind of a specific aromatic diepoxy compound as a part of the cationic polymerizable organic compound in a predetermined amount. It has been found that an optical three-dimensional object that is superior in heat resistance can be obtained while maintaining transparency and yellowing resistance.

  Furthermore, the present inventors include, in the above-described resin composition for optical three-dimensional modeling, containing the specific aromatic triepoxy compound as a cationic polymerizable organic compound in a predetermined ratio, as a part of the cationic polymerizable organic compound. It has been found that when a cationically polymerizable organic compound having a cycloalkene oxide structure in the molecule is further contained in a predetermined amount, the hygroscopic elongation of the three-dimensional structure obtained by optical modeling is reduced and the heat resistance is further improved. It was.

  Furthermore, the present inventors include, as a part of the cationically polymerizable organic compound, in the above-described resin composition for optical three-dimensional modeling that contains the specific aromatic triepoxy compound in a predetermined ratio as the cationically polymerizable organic compound. When the oxetane compound is further added in a predetermined amount, the curing sensitivity by the active energy rays is high, and the shaped article can be produced with high productivity in a reduced active energy ray irradiation time. It has been found that a resin composition for optical three-dimensional modeling can be obtained that provides a three-dimensional model having excellent properties such as excellent, high resolution of the modeled object, excellent modeling accuracy, and low volume shrinkage during curing.

  In addition, the present inventors contain a cationically polymerizable organic compound, a radically polymerizable organic compound, an active energy ray-sensitive cationic polymerization initiator and an active energy ray-sensitive radical polymerization initiator, and are further specified as a cationically polymerizable organic compound. In the above-described resin composition for optical three-dimensional modeling containing an aromatic triepoxy compound in a predetermined ratio, as a radical polymerizable organic compound, an acrylic compound having at least one (meth) acryl group is contained in a predetermined amount Then, the curing sensitivity of the resin composition for optical three-dimensional modeling becomes high, and it is possible to produce a modeled article with high productivity in a shortened active energy ray irradiation time, and it is found that the modeling accuracy is excellent. The present invention has been completed based on various findings.

That is, the present invention
(1) (i) 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) A resin composition for optical three-dimensional modeling;
(Ii) As the cationically polymerizable organic compound (A), the following chemical formula (A-1);

で表されるトリエポキシ化合物（Ａ−１）を、光学的立体造形用樹脂組成物の質量に基づいて５〜５０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。

The resin composition for optical three-dimensional model | molding characterized by containing the triepoxy compound (A-1) represented by these in the ratio of 5-50 mass% based on the mass of the resin composition for optical three-dimensional model | molding. It is.

The present invention also provides:
(2) 30 to 85% by mass of the cationically polymerizable organic compound (A), 10 to 60% by mass of the radically polymerizable organic compound (B) based on the total mass of the resin composition for optical three-dimensional modeling, and active energy The optical three-dimensional structure of (1) above, containing 0.1 to 10% by mass of the radiation-sensitive cationic polymerization initiator (C) and 0.1 to 10% by mass of the active energy ray-sensitive radical polymerization initiator (D). It is a resin composition for modeling.

And this invention
(3) The said (1) or (2) which further contains the nano silica particle (E) with an average particle diameter of 1-200 nm in the ratio of 1-50 mass% based on the total mass of the resin composition for optical three-dimensional modeling. Is a resin composition for optical three-dimensional modeling.
Furthermore, the present invention provides
(4) As a part of the cationically polymerizable organic compound (A), the following general formula (A-2);

（式中、ｍは０〜１０の整数を示す。）
で表されるジエポキシ化合物（Ａ−２）を、光学的立体造形用樹脂組成物の全質量に基づいて２０質量％以下の割合で含有する前記（１）〜（３）のいずれかの光学的立体造形用樹脂組成物である。

(In the formula, m represents an integer of 0 to 10.)
The optical component according to any one of (1) to (3), wherein the diepoxy compound (A-2) represented by the formula (1) is contained at a ratio of 20% by mass or less based on the total mass of the resin composition for optical three-dimensional modeling. It is a resin composition for three-dimensional modeling.

The present invention also provides:
(5) As part of the cationically polymerizable organic compound (A), the epoxy compound (A-3) having a cycloalkene oxide structure in the molecule is 80% by mass based on the mass of the cationically polymerizable organic compound (A). The resin composition for optical three-dimensional modeling according to any one of (1) to (4), which is further contained in the following ratio:
(6) As a part of the cationically polymerizable organic compound (A), an oxetane compound (A-4) having one or more oxetane groups is selected from 5 to 5 based on the mass of the cationically polymerizable organic compound (A). The resin composition for optical three-dimensional modeling according to any one of (1) to (5), further contained in an amount of 50% by mass; and
(7) As the radical polymerizable organic compound (B), an acrylic compound (B-1) having at least one (meth) acryl group is 50% by mass or more based on the mass of the radical polymerizable organic compound (B). The resin composition for optical three-dimensional modeling according to any one of (1) to (6), which is contained in an amount;
It is.
And this invention,
(8) A method for producing a three-dimensional modeled object, wherein optical three-dimensional modeling is performed using the resin composition for optical three-dimensional model modeling according to any one of (1) to (7); and
(9) Optical three-dimensional modeling is performed using the optical three-dimensional model of any one of (1) to (7) to create a three-dimensional model, and the three-dimensional model is subjected to ultraviolet irradiation treatment and / or heat treatment. A method for producing a three-dimensional structure,
It is.

  The resin composition for optical three-dimensional modeling of the present invention comprises a cationic polymerizable organic compound (A), a radical polymerizable organic compound (B), an active energy ray sensitive cationic polymerization initiator (C), and an active energy ray sensitive radical polymerization initiation. In the resin composition for optical three-dimensional modeling containing an agent (D), the triepoxy compound (A-1) represented by the chemical formula (A-1) is added to the mass of the resin composition for optical three-dimensional modeling. Therefore, it has a high thermal deformation temperature and excellent heat resistance, and has a high mechanical strength such as tensile strength and bending strength and an appropriate elongation. In addition, it has excellent toughness, excellent transparency, small discoloration such as yellowing and excellent hue, and produces an optical three-dimensional structure that is maintained even when the excellent transparency and hue are exposed to high temperatures. be able to.

  A cationically polymerizable organic compound comprising 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) The ratio which prescribes | regulates the nano silica particle (E) which has an average particle diameter of nanometer size in this invention in the resin composition for optical three-dimensional model | molding of this invention containing a triepoxy compound (A-1) as (A). The resin composition for optical three-dimensional modeling of the present invention further contained in the above has excellent properties such as mechanical strength such as tensile strength and bending strength, excellent transparency and excellent hue (high yellowing resistance, etc.). While maintaining, an optical three-dimensional molded article having a higher heat distortion temperature and further excellent heat resistance is provided.

  A cationically polymerizable organic compound comprising 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) The resin composition for optical three-dimensional model | molding of this invention containing a triepoxy compound (A-1) as (A), or the optical of this invention containing a triepoxy compound (A-1) and a nano silica particle (E). From the resin composition for optical three-dimensional model | molding of this invention which contains diepoxy compound (A-2) in the quantity prescribed | regulated by this invention as a part of cationically polymerizable organic compound in the resin composition for three-dimensional model | molding, it mentioned above. It is possible to obtain a three-dimensional molded article having excellent mechanical strength, transparency and hue, having a higher heat distortion temperature and superior heat resistance.

  In the above-described resin composition for optical three-dimensional modeling of the present invention, the epoxy compound (A-3) having a cycloalkene oxide structure in the molecule as a part of the cationically polymerizable organic compound (A) is prescribed in the present invention. The resin composition for optical three-dimensional model | molding contained in the ratio of this is further excellent in heat resistance, and gives an optical three-dimensional model | molded article with small hygroscopic elongation.

  In the above-described resin composition for optical three-dimensional modeling of the present invention, the optical three-dimensional modeling containing the oxetane compound (A-4) as a part of the cationically polymerizable organic compound (A) at a predetermined ratio defined in the present invention. In addition to the above-mentioned excellent properties, the resin composition for use has a high curing sensitivity by active energy rays, and can produce a molded article with high productivity in a reduced active energy ray irradiation time. Excellent handleability, high resolution of the modeled object, excellent modeling accuracy, and low volume shrinkage during curing.

  Moreover, in the resin composition for optical three-dimensional model | molding of this invention, the acrylic compound (B-1) which has 1 or more of (meth) acryl groups as a radically polymerizable organic compound (B) is prescribed | regulated by this invention. The resin composition for optical three-dimensional modeling contained at a ratio of 2 is excellent in that the molding sensitivity is high and the modeling object can be produced with high productivity in a shortened active energy ray irradiation time, and the modeling accuracy is improved. Has characteristics.

FIG. 1 is a graph showing the measurement results of the total light transmittance of the three-dimensional structure obtained in Example 1, Example 5 and Comparative Example 1. FIG. 2 is a graph showing the measurement results of the yellowness of the three-dimensional structure obtained in Example 1, Example 5 and Comparative Example 1. FIG. 3 is a photograph after post-curing the three-dimensional structure obtained in Example 1, Example 5 and Comparative Example 1 with ultraviolet rays, and a photograph after further heat treatment, and FIG. Is a photograph of the three-dimensional structure of Example 1, the upper part is a photograph of the three-dimensional object that has been post-cured with ultraviolet rays at room temperature, and the lower part is a photograph of the three-dimensional object that was further heat-treated at 120 ° C. for 2 hours. FIG. 3 (b) is a photograph of the three-dimensional structure of Example 5, wherein the upper part is a photograph of the three-dimensional object that has been post-cured with ultraviolet rays at room temperature, and the lower part is further heat-treated at 140 ° C. for 2 hours. FIG. 3C is a photograph of the three-dimensional structure of Comparative Example 1, in which the upper part is a photograph of the three-dimensional object that has been post-cured with ultraviolet rays at room temperature, and the lower part is 120 after that. It is a photograph of the three-dimensional molded item heat-processed at 2 degreeC for 2 hours.

The present invention is described in detail below.
The resin composition for optical three-dimensional model | molding of this invention irradiates the active energy ray (an ultraviolet ray, an electron beam, X-rays, radiation, high frequency etc.) which can harden the resin composition for optical three-dimensional model | molding, and three-dimensional solid. It is the resin composition used for manufacturing a molded article.
The resin composition for optical three-dimensional model | molding of this invention contains a cationically polymerizable organic compound (A) and a radically polymerizable organic compound (B) as an active energy ray polymeric compound superposed | polymerized by irradiation of an active energy ray.

  The cationically polymerizable organic compound (A) used in the present invention is a compound that causes a polymerization reaction and / or a crosslinking reaction when irradiated with an active energy ray in the presence of an active energy ray-sensitive cationic polymerization initiator (C). The resin composition for optical three-dimensional modeling of the present invention has the following chemical formula (A-1) as at least a part of the cationically polymerizable organic compound (A);

で表されるトリエポキシ化合物（Ａ−１）を含有することが必要である。

It is necessary to contain the triepoxy compound (A-1) represented by these.

  The triepoxy compound (A-1) represented by the chemical formula (A-1) has a compound name of “2- (4-glycidyloxyphenyl) -2- [4- [1,1-bis (4- Glycidyloxyphenyl) ethyl] phenyl] propane ”or“ 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4-([2,3-epoxypropoxy] ]] Phenyl)] ethyl] phenyl] propane "aromatic triepoxy compound (aromatic triglycidyloxy compound), for example," Techmore VG3101L "(trade name) (manufactured by Printec Co., Ltd.) .

  Since the resin composition for optical three-dimensional modeling of the present invention contains a triepoxy compound (A-1) as the cationic polymerizable organic compound (A), the heat distortion temperature is high, the heat resistance is excellent, and the tensile strength is high. It has high mechanical strength such as strength and bending strength and has an appropriate elongation, excellent toughness, excellent transparency, small discoloration such as yellowing, excellent hue, and excellent transparency and An optical three-dimensional object that is maintained even when the hue is exposed to a high temperature is obtained.

The content ratio of the triepoxy compound (A-1) in the resin composition for optical three-dimensional modeling of the present invention is high in heat distortion temperature, excellent in heat resistance, excellent in mechanical strength such as tensile strength and bending strength, and tough. In addition, the mass of the resin composition for optical three-dimensional modeling (total mass) from the viewpoint of obtaining a three-dimensional model that is excellent in transparency and hue and that is maintained even when the excellent transparency and hue are exposed to high temperatures. ) To 5 to 50% by mass, preferably 5 to 40% by mass, and more preferably 8 to 35% by mass.
If the content ratio of the triepoxy compound (A-1) is too small, the thermal deformation temperature of the optical three-dimensional structure is lowered, and mechanical strength such as tensile strength and bending strength, toughness and the like are lowered. On the other hand, when the content ratio of the triepoxy compound (A-1) is too large, the viscosity of the resin composition for optical three-dimensional modeling becomes high and the handling property becomes inferior, or in the resin composition for optical three-dimensional modeling This causes problems such as difficulty in dissolving the triepoxy compound (A-1).

In the resin composition for optical three-dimensional model | molding of this invention, the whole quantity of the cationically polymerizable organic compound (A) contained in the said composition may consist of a triepoxy compound (A-1), or cationic polymerization. Triepoxy compound (A-1) may be contained as part of the organic compound (A). Among these, the resin composition for optical three-dimensional model | molding of this invention contains other cation polymerizable organic compounds with a triepoxy compound (A-1) as a cation polymerizable organic compound (A), Since the handling property at the time of optical modeling of the optical three-dimensional modeling resin composition, photocuring sensitivity, modeling accuracy, water resistance, moisture resistance, dimensional accuracy, and the like of the resulting three-dimensional model are improved, it is preferable.
As the other cationically polymerizable organic compound, any of the cationically polymerizable organic compounds used in the resin composition for optical three-dimensional modeling can be used. As a representative example, a triepoxy compound (A-1 ), An epoxy compound, a cyclic ether compound, a cyclic acetal compound, a cyclic lactone compound, a cyclic thioether compound, a spiro orthoester compound, a vinyl ether compound, and the like. In the present invention, one or more of the above cationic polymerizable organic compounds can be contained as the other cationic polymerizable organic compound.

Specific 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:
(1) Epoxy compounds such as aromatic epoxy compounds, alicyclic epoxy compounds, and aliphatic epoxy compounds other than the triepoxy compound (A-1);
(2) Trimethylene oxide, oxetane compounds, oxolane compounds such as tetrahydrofuran, 2,3-dimethyltetrahydrofuran, cyclic ethers or cyclic acetal compounds such as trioxane, 1,3-dioxolane, 1,3,6-trioxane cyclooctane ;
(3) cyclic lactone compounds such as β-propiolactone and ε-caprolactone;
(4) thiirane compounds such as ethylene sulfide and thioepichlorohydrin;
(5) Thietane compounds such as 1,3-propyne sulfide, 3,3-dimethylthietane;
(6) Vinyl ether compounds such as ethylene glycol divinyl ether, alkyl vinyl ether, 3,4-dihydropyran-2-methyl (3,4-dihydropyran-2-carboxylate), triethylene glycol divinyl ether;
(7) Spiro orthoester compound obtained by reaction of epoxy compound and lactone;
And so on.

  Among these, in the present invention, an epoxy compound other than the triepoxy compound (A-1) and an oxetane compound are preferably used as the other cationically polymerizable organic compound. As an epoxy compound other than the triepoxy compound (A-1), a polyepoxy compound having two or more epoxy groups in one molecule is more preferably used, and a monooxetane compound having one oxetane group as the oxetane compound. And one or both of polyoxetane compounds having two or more oxetane groups are preferably used.

  Examples of aromatic epoxy compounds other than the triepoxy compound (A-1) mentioned in (1) above that can be used as other cationically polymerizable organic compounds include, for example, monovalent or polyvalent compounds having at least one aromatic nucleus. Examples thereof include mono- or polyglycidyl ethers of phenols or alkylene oxide adducts thereof. Specific examples include glycidyl ethers and epoxy novolacs obtained by the reaction of bisphenol A, bisphenol F or alkylene oxide adducts thereof with epichlorohydrin. Resin, phenol, cresol, butylphenol or monoglycidyl ether of polyether alcohol obtained by adding alkylene oxide to these, diepoxy compound (A-2) represented by the following general formula (A-2) Etc. can be mentioned.

（式中、ｍは０〜１０の整数を示す。）

(In the formula, m represents an integer of 0 to 10.)

The diepoxy compound (A-2) represented by the general formula (A-2) is a diepoxy compound having a fluorene skeleton.
In said general formula (A-2), m is an integer of 0-10, From the point that the heat resistance of the three-dimensional molded item obtained from the resin composition for optical three-dimensional modeling becomes more excellent, m Is preferably 0 to 4, more preferably 0 to 2, and still more preferably 0.

In the above general formula (A-2), the diepoxy compound in which m is 0 is represented by the following chemical formula (A-2a), and is generally referred to as “bisphenol fluorenediglycidyl ether”. PG-100 "(trade name) (manufactured by Osaka Gas Chemical Co., Ltd.).
Further, in the general formula (A-2), a diepoxy compound in which m is 1 or more is represented by the following chemical formula (A-2b), and is generally referred to as “bisphenoxyethanol fluorenediglycidyl ether”. It is sold as “On Coat EX-1020” (trade name) (manufactured by Osaka Gas Co., Ltd.).

When the diepoxy compound (A-2) is contained as a part of the cationically polymerizable organic compound (A) in the resin composition for optical three-dimensional modeling of the present invention, the content ratio of the diepoxy compound (A-2) Is preferably 20% by mass or less, and more preferably 15% by mass or less, based on the mass of the resin composition for optical three-dimensional modeling.
When the diepoxy compound (A-2) is contained in the resin composition for optical three-dimensional modeling according to the present invention together with the triepoxy compound (A-1) at a ratio of 20% by mass or less, the optical three-dimensional modeling is performed. While maintaining the transparency, hue, and mechanical properties of the obtained optical three-dimensional model well, the heat distortion temperature of the optical three-dimensional model becomes higher and the heat resistance is further improved.
When the content ratio of the diepoxy compound (A-2) is larger than the above, the transparency of the optical three-dimensional structure is lowered, and discoloration such as yellowing is increased.

Examples of the alicyclic epoxy compounds mentioned in the above (1) that can be used as other cationically polymerizable organic compounds include compounds having a cycloalkene structure such as cyclohexene or cyclopentene ring-containing compounds such as hydrogen peroxide and peracid. And an epoxy compound having a cycloalkene oxide structure obtained by epoxidation with an appropriate oxidizing agent, and a polyglycidyl ether of a polyhydric alcohol having at least one alicyclic ring.
As used herein, “cycloalkene oxide structure” refers to “a structure in which an unsaturated double bond moiety in a cycloalkene ring is oxidized (epoxidized)”.

  When the resin composition for optical three-dimensional modeling of the present invention contains another cationic polymerizable organic compound together with the triepoxy compound (A-1), a cycloalkene oxide structure is used as the other cationic polymerizable organic compound. An epoxy compound contained in the molecule [hereinafter referred to as “cycloalkene oxide structure-containing epoxy compound (A-3)]” is preferably used, and in particular, an epoxy compound having two or more epoxy groups based on the cycloalkene oxide structure in one molecule. Preferably used. When the resin composition for optical three-dimensional modeling of the present invention contains the cycloalkene oxide structure-containing epoxy compound (A-3) as a part of the cationically polymerizable organic compound (A), the resin for optical three-dimensional modeling The photocuring sensitivity of the composition is improved.

Representative examples of the cycloalkene oxide structure-containing epoxy compound (A-3) include cyclobutene oxide structure, cyclopentene oxide structure, cyclohexene oxide structure, cycloheptene oxide structure, cyclooctene oxide structure, cyclodecene oxide structure, and cyclododecene. Mention may be made of epoxy compounds having one or more of C 4-12 cycloalkene oxide structures such as oxide structures in the molecule. At that time, the carbon atom forming the cycloalkane ring in the cycloalkene oxide structure may not be substituted, or one or more of the carbon atoms forming the cycloalkane ring are substituted. In addition, the bond of the carbon atom forming the cycloalkane ring may be bonded to another group in the organic compound or may be bonded to another structural part to form a condensed ring. May be.
Furthermore, in the cycloalkene oxide structure-containing epoxy compound (A-3), the location (bonding position) and the number (bonding number) of the “cycloalkene oxide structure” are not particularly limited.

  Although it is not limited, in the resin composition for optical three-dimensional modeling of the present invention, a specific example of the cycloalkene oxide structure-containing epoxy compound (A-3) preferably used as a part of the cationically polymerizable organic compound (A) Examples include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene dioxide, 4-vinylepoxycyclohexane, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3 , 4-Epoxy-6-methylcyclohexane Suncarboxylate, methylenebis (3,4-epoxycyclohexane), di (3,4-epoxycyclohexylmethyl) ether of ethylene glycol, ethylenebis (3,4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, epoxy Examples thereof include di-2-ethylhexyl hexahydrophthalate, dicyclopentadiene diepoxide, and epoxy compounds represented by the following chemical formulas (A-3a) to (A-3h).

［上記の式（Ａ−３ｈ）中、Ｒ¹は、水素原子または炭素数１〜３のメチル基、エチル基、ｎ−プロピル基またはイソプロピル基を示す。］

[In said formula (A-3h), R < ¹ > shows a hydrogen atom or a C1-C3 methyl group, an ethyl group, n-propyl group, or an isopropyl group. ]

In the present invention, one or more of the compounds exemplified above can be used as the cycloalkene oxide structure-containing epoxy compound (A-3).
Among them, in the present invention, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate is easily available as the cycloalkene oxide structure-containing epoxy compound (A-4), and it is formed by stereolithography. It is preferably used because it greatly contributes to the improvement of the heat resistance of the three-dimensional molded article obtained in this way.

When the cycloalkene oxide structure-containing epoxy compound (A-3) is contained as a part of the cationically polymerizable organic compound (A) in the optical three-dimensional modeling resin composition of the present invention, the cycloalkene oxide structure-containing epoxy The content of the compound (A-3) is based on the mass of the cationic polymerizable organic compound (A) [the total mass of all cationic polymerizable organic compounds (A) contained in the resin composition for optical three-dimensional modeling]. 80 mass% or less, preferably 10 to 70 mass%, more preferably 10 to 50 mass%.
When the content of “cycloalkene oxide structure-containing epoxy compound (A-3)” is excessively large, the hygroscopic elongation of the three-dimensional structure obtained by optical modeling becomes large, and the dimensional stability is lowered.

  Specific examples of the above-mentioned “polyglycidyl ether of polyhydric alcohol having at least one alicyclic ring” which can be used as other cationically polymerizable organic compounds include hydrogenation represented by the following general formula: Bisphenol diglycidyl ether and the like can be mentioned.

（式中、Ｒ²は水素原子またはメチル基を示す。）
本発明の光学的立体造形用樹脂組成物中に、カチオン重合性有機化合物（Ａ）の一部として水素添加ビスフェノール系ジグリシジルエーテルを含有させた場合には、光学的立体造形用樹脂組成物を高湿度下においても水分や湿分の吸収が少なくて高い硬化感度が維持されると共に、厚膜硬化性、解像度、紫外線透過性、可撓性などが良好になり、更に光造形して得られる立体造形物の体積収縮率を低くすることができる。

(In the formula, R ² represents a hydrogen atom or a methyl group.)
When the hydrogenated bisphenol diglycidyl ether is contained as part of the cationically polymerizable organic compound (A) in the resin composition for optical three-dimensional modeling of the present invention, the resin composition for optical three-dimensional modeling is used. Even under high humidity, moisture and moisture absorption is low and high curing sensitivity is maintained. Thick film curability, resolution, UV transparency, flexibility, etc. are improved, and it is obtained by stereolithography. The volumetric shrinkage of the three-dimensional structure can be reduced.

  Specific examples of the hydrogenated bisphenol-based diglycidyl ether include hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, and hydrogenated bisphenol Z diglycidyl ether. In the present invention, as the hydrogenated bisphenol-based diglycidyl ether, only one kind of the aforementioned diglycidyl ether may be used, or two or more kinds may be used in combination. Among them, as the hydrogenated bisphenol-based diglycidyl ether, hydrogenated bisphenol A diglycidyl ether is preferably used in terms of availability, moisture absorption resistance of a three-dimensional model, and the like.

  When the hydrogenated bisphenol diglycidyl ether is contained as part of the cationically polymerizable organic compound (A) in the resin composition for optical three-dimensional modeling of the present invention, the content of the hydrogenated bisphenol diglycidyl ether is Based on the mass of the cationic polymerizable organic compound (A) [total mass of all cationic polymerizable organic compounds (A) contained in the resin composition for optical three-dimensional modeling] Preferably, it is 5-60 mass%, More preferably, it is 10-50 mass%.

  Examples of the aliphatic epoxy resin mentioned in the above (1) that can be used as other cationically polymerizable organic compounds include, for example, polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof, and aliphatic long-chain polybases. Examples thereof include polyglycidyl esters of acids, homopolymers and copolymers of glycidyl acrylate and glycidyl methacrylate. More specifically, for example, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, sorbitol tetraglycidyl ether, Adding one or more alkylene oxides to aliphatic polyhydric alcohols such as hexaglycidyl ether of dipentaerythritol, diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, ethylene glycol, propylene glycol, glycerin Polyglycidyl ether of polyether polyol obtained by the above, diglycidyl ester of aliphatic long-chain dibasic acid, and the like. In addition to the above epoxy compounds, for example, monoglycidyl ethers of higher aliphatic alcohols, glycidyl esters of higher fatty acids, epoxidized soybean oil, butyl epoxy stearate, octyl epoxy stearate, epoxidized linseed oil, epoxidized polybutadiene And so on.

Moreover, when other cationically polymerizable organic compounds are contained in the resin composition for optical three-dimensional modeling of this invention with a triepoxy compound (A-1), as said other cationically polymerizable organic compound, (2 The oxetane compound [hereinafter referred to as “oxetane compound (A-4)”] mentioned in (1) is preferably used. As the oxetane compound (A-4), any of a monooxetane compound having one oxetane group in the molecule and a polyoxetane compound having two or more oxetane groups in the molecule can be used.
By including the oxetane compound (A-4) in the resin composition for optical three-dimensional modeling of the present invention, the viscosity of the resin composition for optical three-dimensional modeling becomes low, and it becomes easy to perform the optical modeling work. While the photocuring sensitivity of the resin composition for three-dimensional modeling becomes high, the photo-molding time when producing the three-dimensional model can be shortened, and the high photocuring sensitivity of the resin composition for three-dimensional modeling is maintained high for a long time. The heat resistance of the three-dimensional model formed from the optical three-dimensional model resin composition can be further improved.

In this case, any monooxetane compound can be used as long as it has one oxetane group in one molecule, and in particular, it has one oxetane group and one alcoholic hydroxyl group in one molecule. A monooxetane monoalcohol compound is preferably used.
Among such monooxetane monoalcohol compounds, the monooxetane monoalcohol compound (A-4a ₁ ) represented by the following general formula (A-4a ₁ ) and the following general formula (A-4a ₂ ) At least one of the represented monooxetane monoalcohol compounds (A-4a ₂ ) is more preferably used as a monooxetane compound from the viewpoints of availability, high reactivity, and low viscosity.

（式中、Ｒ³およびＲ⁴は炭素数１〜５のアルキル基、Ｒ⁵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。）

(In the formula, R ³ and R ⁴ represent an alkyl group having 1 to 5 carbon atoms, and R ⁵ represents an alkylene group having 2 to 10 carbon atoms which may have an ether bond.)

In the above general formula (A-4a ₁ ), examples of R ³ include methyl, ethyl, propyl, butyl, and pentyl.
Specific examples of monooxetane alcohol (A-4a ₁ ) include 3-hydroxymethyl-3-methyloxetane, 3-hydroxymethyl-3-ethyloxetane, 3-hydroxymethyl-3-propyloxetane, and 3-hydroxymethyl- 3-normal butyl oxetane, 3-hydroxymethyl-3-propyl oxetane, etc. can be mentioned, These 1 type (s) or 2 or more types 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 (A-4a ₂ ), examples of R ⁴ include methyl, ethyl, propyl, butyl, and pentyl.
In the above general formula (A-4a ₂ ), R ⁵ 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 ⁵ include ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, and 3-oxypentylene group. Among these, R ⁵ 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.

  As the polyoxetane compound, any of a compound having two oxetane groups in the molecule, a compound having three or more oxetane groups, and a compound having four or more oxetane groups can be used, and among them, dioxetane having two oxetane groups. A compound is preferably used. As a dioxetane compound, the following general formula (A-4b);

（式中、２個のＲ⁶は互いに同じかまたは異なる炭素数１〜５のアルキル基、Ｒ⁷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、ｎは０または１を示す。）
で表されるジオキセタン化合物（Ａ−４ｂ）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（Ａ−４ｂ）において、Ｒ⁶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、Ｒ⁷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）、フェニレン基、式：−ＣＨ₂−Ｐｈ−ＣＨ₂−または−ＣＨ₂−Ｐｈ−Ｐｈ−ＣＨ₂−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などを挙げることができる。

(Wherein two R ⁶ are the same or different alkyl groups having 1 to 5 carbon atoms, R ⁷ is a divalent organic group having or not having an aromatic ring, and n is 0 or 1) Is shown.)
The dioxetane compound (A-4b) represented by the formula is preferably used in terms of availability, reactivity, low hygroscopicity, mechanical properties of the cured product, and the like.
In the above general formula (A-4b), examples of R ⁶ include methyl, ethyl, propyl, butyl, and pentyl. Examples of R ⁷ 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.), phenylene group, divalent group represented by the formula: —CH ₂ —Ph—CH ₂ — or —CH ₂ —Ph—Ph—CH ₂ —, hydrogenated bisphenol A residue, hydrogenated bisphenol F residue Group, hydrogenated bisphenol Z residue, cyclohexanedimethanol residue, tricyclodecanedimethanol residue and the like.

Specific examples of the dioxetane compound (A-4b) include a dioxetane compound represented by the following formula (A-4b ₁ ) or formula (A-4b ₂ ).

（式中、２個のＲ⁶は互いに同じかまたは異なる炭素数１〜５のアルキル基、Ｒ⁷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 ⁶ are the same or different alkyl groups having 1 to 5 carbon atoms, and R ⁷ is a divalent organic group having or not having an aromatic ring.)

Specific examples of the dioxetane compound represented by the above formula (A-4b 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 the above formula (A-4b ₂₎ are two R ⁶ are both methyl in the above formula (A-4b _2), ethyl, propyl, butyl or pentyl group R ⁷ is ethylene group, propylene group, butylene group, neopentylene group, n-pentamethylene group, n-hexamethylene group, etc.), phenylene group, formula: —CH ₂ —Ph—CH ₂ — or —CH ₂ — Divalent group represented by Ph—Ph—CH ₂ —, hydrogenated bisphenol A residue, hydrogenated bisphenol F residue, hydrogenated bisphenol Z residue, cyclohexanedimethanol residue, tricyclodecanedimethanol residue The dioxetane compound which is can be mentioned.

  The resin composition for optical three-dimensional modeling of the present invention may contain only a monooxetane compound as the oxetane compound (A-4), or may contain only a polyoxetane compound such as a dioxetane compound. Or may contain both a monooxetane compound and a polyoxetane compound, and it contains both a monooxetane compound and a polyoxetane compound (particularly a dioxetane compound) from the viewpoint of heat resistance and photocurability. preferable.

When the oxetane compound (A-4) is contained as a part of the cationically polymerizable organic compound (A) in the resin composition for optical three-dimensional modeling of the present invention, the content of the oxetane compound (A-4) is: It is preferably 5 to 50% by mass based on the mass of the cationically polymerizable organic compound (A) [total mass of all cationically polymerizable organic compounds (A) contained in the resin composition for optical three-dimensional modeling]. 10 to 40% by mass, more preferably 10 to 30% by mass.
If the content of the oxetane compound (A-4) is excessively increased, the curing sensitivity of the resin composition for optical three-dimensional modeling is usually improved, but the elastic modulus, strength, etc. of the three-dimensional model are lowered and shape retention is reduced. I may lose.

  The resin composition for optical three-dimensional modeling of the present invention includes a diepoxy compound (A-2) and a cycloalkene oxide structure-containing epoxy compound (A) as a cationically polymerizable organic compound (A) together with a triepoxy compound (A-1). -3), may contain one of hydrogenated bisphenol diglycidyl ether and oxetane compound (A-4), or may contain two [ie, cycloalkene oxide structure] -Containing epoxy compound (A-3) and hydrogenated bisphenol-based diglycidyl ether, cycloalkene oxide structure-containing epoxy compound (A-3) and oxetane compound (A-4) or hydrogenated bisphenol-based diglycidyl It may contain two kinds of ether and oxetane compound (A-4)], or cycloa Ken oxide structure-containing epoxy compound (A-3), it may contain three hydrogenated bisphenol-based diglycidyl ether and oxetane compound (A-4).

  When the resin composition for optical three-dimensional model | molding of this invention contains another cationically polymerizable organic compound other than that with a triepoxy compound (A-1) as a cationically polymerizable organic compound (A), others The content of the cationically polymerizable organic compound is preferably 75% by mass or less, more preferably 20 to 70% by mass, with respect to the total mass of the resin composition for optical three-dimensional modeling, 25 More preferably, it is -60 mass%.

The radical polymerizable organic compound (B) used in the present invention has an active energy ray in the presence of an active energy ray sensitive radical polymerization initiator (D) [hereinafter sometimes simply referred to as “radical polymerization initiator (D)”]. It is a compound that causes a polymerization reaction and / or a crosslinking reaction when irradiated.
Since the resin composition for optical three-dimensional modeling of the present invention contains the radical polymerizable organic compound (B), the viscosity is low, the handleability is excellent, and the photocuring sensitivity is high, so that the three-dimensional model is shortened. It can be manufactured smoothly in the optical modeling time, and the dimensional accuracy, mechanical properties, surface smoothness, hardness, etc. of the three-dimensional model to be obtained are good.

As the radically polymerizable organic compound (B), any of the radically polymerizable organic compounds conventionally used in the resin composition for optical three-dimensional modeling can be used. Typical examples include (meth) acrylate compounds, An unsaturated polyester compound, an allyl urethane type compound, etc. can be mentioned, These 1 type (s) or 2 or more types can be used.
Among them, as the radical polymerizable organic compound (B), an acrylic compound (B-1) having at least one (meth) acryl group in one molecule is preferably used. In the resin composition for optical three-dimensional modeling of the present invention, the acrylic compound (B-1) is replaced with the mass of the radical polymerizable organic compound (B) [total radical polymerizable organic contained in the resin composition for optical three-dimensional modeling. Based on the total mass of the compound (B)], the content is preferably 50% by mass or more, more preferably 80% by mass or more, and the proportion of 90 to 100% by mass. It is further preferable to contain.
Specific examples of the acrylic compound (B-1) include a reaction product of an epoxy compound and (meth) acrylic acid, a (meth) acrylic acid ester of an alcohol, a polyester (meth) acrylate, and a polyether (meth) acrylate. And so on.

  The reaction product of the above-described epoxy compound that can be used as the radical polymerizable organic compound (B) and (meth) acrylic acid includes an aromatic epoxy compound, an alicyclic epoxy compound and / or an aliphatic epoxy compound, and (meta ) Epoxy (meth) acrylate reaction products obtained by reaction with acrylic acid. As a specific example, an epoxy obtained by reacting a glycidyl ether obtained by reacting a bisphenol compound such as bisphenol A or bisphenol F or an alkylene oxide adduct thereof with an epoxidizing agent such as epichlorohydrin with (meth) acrylic acid. (Meth) acrylate, epoxy novolac resin and epoxy (meth) acrylic acid such as epoxy (meth) acrylate reaction product obtained by reacting (meth) acrylic acid and epoxy (meth) ) Acrylate reaction products.

Examples of the (meth) acrylic acid esters of the alcohols that can be used as the radical polymerizable organic compound (B) include aromatic alcohols, aliphatic alcohols, alicyclic alcohols having at least one hydroxyl group in the molecule, and Examples thereof include (meth) acrylates obtained by reacting these alkylene oxide adducts 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 tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate and other dipentaerythritol poly (meth) acrylates, diols, triols, tetraols, hexaols described above And (meth) acrylates of alkylene oxide adducts of polyhydric alcohols, such as ethylene oxide-modified bisphenol A diacrylate and propylene oxide-modified bisphenol A diacrylate.
Among them, (meth) acrylates of alcohols include (meth) acrylates having two or more (meth) acrylic groups in one molecule obtained by reaction of polyhydric alcohol and (meth) acrylic acid, for example di- Pentaerythritol poly (meth) acrylate, pentaerythritol tetra (meth) acrylate, poly (meth) acrylate of ethoxylated pentaerythritol and the like are preferably used.
Of the (meth) acrylate compounds described above, an acrylate compound is preferably used in view of the polymerization rate rather than a methacrylate compound.

Furthermore, examples of the above-described polyester (meth) acrylate that can be used as the radical polymerizable organic compound (B) 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.

  In the resin composition for optical three-dimensional modeling of the present invention, dipentaerythritol polyacrylates such as dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate, ethylene oxide modified pentaerythritol tetraacrylate, ethylene oxide are used as the radical polymerizable organic compound (B). Polyacrylates of alkylene oxide-modified polyhydric alcohols (such as alkylene oxide-modified pentaerythritol and trimethylolpropane) such as modified trimethylolpropane triacrylate, propylene oxide-modified pentaerythritol tetraacrylate, propylene oxide-modified trimethylolpropane triacrylate, bisphenol A di Epoxy acid obtained by reacting glycidyl ether with acrylic acid One or more of the rate (for example, “VR-77” manufactured by Showa Polymer Co., Ltd.), isobornyl acrylate, lauryl acrylate, isostearyl acrylate, etc. are reactive, the mechanical properties of the three-dimensional model, etc. From this point, it is preferably used. In order to obtain a three-dimensional molded article having excellent heat resistance, a compound having two or more (meth) acryl groups is added to the resin composition for optical three-dimensional modeling based on the mass of the radical polymerizable organic compound (B). It is preferable to make it contain in the ratio of 50 mass% or more, and it is preferable to make it contain in the ratio of 60 mass% or more.

In the present invention, as the active energy ray-sensitive cationic polymerization initiator (C) [hereinafter sometimes simply referred to as “cationic polymerization initiator (C)”], the cationically polymerizable organic compound (A) when irradiated with active energy rays. Any of the polymerization initiators capable of initiating cationic polymerization of can be used.
Among them, as the cationic polymerization initiator (C), 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. Specifically, for example, triarylsulfonium hexafluoroantimonate, triphenylphenacylphosphonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, bis- [4- (diphenylsulfonio) phenyl] sulfide bisdihexa Fluoroantimonate, bis- [4- (di4′-hydroxyethoxyphenylsulfonio) phenyl] sulfide bisdihexafluoroantimonate, bis- [4- (diphenylsulfonio) phenyl] sulfide bisdihexafluorophos Fate, diphenyliodonium tetrafluoroborate and the like can be mentioned.
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 (C) as necessary.

  In the present invention, as the active energy ray-sensitive radical polymerization initiator (D) [hereinafter sometimes simply referred to as “radical polymerization initiator (D)”], the radical polymerizable organic compound (B) when irradiated with active energy rays. Any of the polymerization initiators capable of initiating radical polymerization of benzyl or its dialkyl acetal compounds, phenyl ketone compounds, acetophenone compounds, benzoin or its alkyl ether compounds, benzophenone compounds, thioxanthone compounds can be used. A compound etc. can be mentioned.

Specifically, examples of benzyl or a dialkyl acetal compound thereof include benzyl dimethyl ketal and benzyl-β-methoxyethyl acetal.
Examples of phenyl ketone compounds 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 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, or 2 or more types of radical polymerization initiator (D) can be mix | blended and used according to desired performance.
Among them, in the present invention, 1-hydroxycyclohexyl phenyl ketone is preferably used as the radical polymerization initiator (D) because the resulting three-dimensional model has a small yellowness and an excellent hue.

  The resin composition for optical three-dimensional modeling of the present invention includes the viscosity, reaction rate, modeling speed, thermal deformation temperature (heat resistance), mechanical strength, toughness, durability, dimensional accuracy of the three-dimensional model obtained. In view of the above, based on the total mass of the resin composition for optical three-dimensional modeling, cationically polymerizable organic compound (A) [all cationic polymerizable organic compounds (A) contained in the resin composition for optical three-dimensional modeling] Of the radically polymerizable organic compound (B) [all contained in the resin composition for optical three-dimensional modeling] containing 30 to 85% by mass, further 40 to 80% by mass, particularly 50 to 78% by mass. Of the radical polymerizable organic compound (B)] in an amount of 10 to 60% by mass, further 10 to 50% by mass, particularly 15 to 40% by mass, and 0.1 to 10% of the cationic polymerization initiator (C). % By mass, further 1-8% by mass, especially 1-5% by mass It contains a radical polymerization initiator (D) 0.1 to 10 mass%, further 1 to 8 wt%, and preferably in a proportion of particularly 1-7% by weight.

  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 two or more of an inhibitor, a filler (crosslinked polymer particles, silica, glass powder, ceramic powder, metal powder, etc.), and a modifying resin may be contained.

In particular, the resin composition for optical three-dimensional modeling that further contains nano silica particles having an average particle size of nanometer size in the resin composition for optical three-dimensional modeling of the present invention is excellent in mechanical properties and excellent. While maintaining an excellent hue with little discoloration such as transparency and yellowing, it is possible to obtain an optical three-dimensional object having a higher heat deformation temperature and further excellent heat resistance, and the optical three-dimensional object is, for example, 140 ° C. Even when exposed to extremely high temperatures, the transparency is maintained and the increase in yellowing is extremely small.
Nanosilica particles having an average particle diameter of 1 to 200 nm in terms of dispersibility in the resin composition for optical three-dimensional modeling, availability, transparency of the optical three-dimensional modeled product, heat resistance, etc. Are preferred, those with 1 to 100 nm are more preferred, those with 2 to 50 nm are more preferred, and those with 5 to 30 nm are particularly preferred.
Here, the average particle diameter of the nanosilica particles in this specification refers to the average particle diameter measured by the neutron small angle scattering method (SANS), and the specific measurement method is as described in the following examples.

The nanosilica particles (E) are nanosilica particles or nanosilica particle-containing materials that can be uniformly dispersed in the optical three-dimensional modeling resin composition in a monodispersed state without causing aggregation between the nanosilica particles. Any of them can be used, and the method for preparing the nanosilica particles (E) is not particularly limited.
Although not limited, examples of the nanosilica particles (E) (nanosilica particle dispersion) that can be preferably used in the present invention include, for example, nanosilica particles that have been surface-treated so that aggregation between the nanosilica particles does not occur, and the nanosilica Examples thereof include nano silica particle dispersions in which particles are dispersed and contained in a cationically polymerizable organic compound or a radically polymerizable organic compound.

Specific examples of the nano silica particles (E) preferably used in the present invention are all products of Nano Resin (Germany),
(A) “Nanopox A 610” (dispersion of nanosilica particles in which nanosilica particles having an average particle diameter of about 20 nm are dispersed in an alicyclic branch polymer, content of nanosilica particles = 40% by mass);
(B) “Nanopox A 660” [Dispersion of nanosilica particles in which nanosilica particles having an average particle diameter of about 20 nm are dispersed in 3-hydroxymethyl-3-ethyloxetane (reactive diluent), inclusion of nanosilica particles Amount = 50 mass%]
(C) “Nanopox E 470” (dispersion of nanosilica particles in which nanosilica particles having an average particle diameter of about 20 nm are dispersed in bisphenol A diglycidyl ether, content of nanosilica particles = 40% by mass)
(D) “Nanocryl A 370” (dispersion of nanosilica particles in which nanosilica particles having an average particle diameter of about 20 nm are dispersed in hydroxymethyl methacrylate, content of nanosilica particles = 50 mass%);
(E) “Nanocryl A 200” (dispersion of nanosilica particles in which nanosilica particles having an average particle diameter of about 20 nm are dispersed in trimethylolpropane formal acrylate, content of nanosilica particles = 50 mass%);
(F) “Nanocryl A 210” (dispersion of nanosilica particles in which nanosilica particles having an average particle diameter of about 20 nm are dispersed in hexanediol diacrylate, content of nanosilica particles = 50 mass%);
(G) “Nanocryl A 215” (dispersion of nanosilica particles in which nanosilica particles having an average particle diameter of about 20 nm are dispersed in tripropylene glycol diacrylate, content of nanosilica particles = 50 mass%);
(H) “Nanocryl A 216” (dispersion of nanosilica particles in which nanosilica particles having an average particle diameter of about 20 nm are dispersed in propoxylated neopentylglycol diacrylate, content of nanosilica particles = 50 mass%);
(I) “Nanocryl A 220” (dispersion of nanosilica particles in which nanosilica particles having an average particle diameter of about 20 nm are dispersed in trimethylolpropane triacrylate, content of nanosilica particles = 50% by mass);
(J) “Nanocryl A 223” (dispersion of nanosilica particles in which nanosilica particles having an average particle diameter of about 20 nm are dispersed in ethoxylated trimethylolpropane triacrylate, content of nanosilica particles = 50% by mass);
(K) “Nanocryl A 225” (dispersion of nanosilica particles in which nanosilica particles having an average particle diameter of about 20 nm are dispersed in propoxylated glycerin triacrylate, content of nanosilica particles = 50% by mass);
(L) “Nanocryl A 235” (dispersion of nanosilica particles in which nanosilica particles having an average particle diameter of about 20 nm are dispersed in alkoxylated pentaerythritol tetraacrylate, content of nanosilica particles = 50 mass%);
And so on.
In the above-mentioned nanosilica particles (a dispersion of nanosilica particles) manufactured by Nanoresin, the nanosilica particles are surface-modified so as not to aggregate.

When the nanosilica particles (E) are contained in the resin composition for optical three-dimensional modeling of the present invention, the content of the nanosilica particles (E) itself is based on the total mass of the resin composition for optical three-dimensional modeling, It is preferably 1 to 50% by mass, more preferably 5 to 40% by mass, still more preferably 5 to 30% by mass, and particularly preferably 5 to 20% by mass.
When the content of the nanosilica particles (E) is excessively large, the flexibility of the three-dimensional structure obtained by optical three-dimensional modeling is lowered, or the light transmittance is easily lowered.

The method for preparing the resin composition for optical three-dimensional modeling of the present invention is not particularly limited, and the cationic polymerizable organic compound (A), the radical polymerizable organic compound (B), the cationic polymerization initiator (C), and the radical polymerization initiator. It may be prepared by any method as long as it is a method capable of obtaining a composition in which (D) and the nanosilica particles (E) used as necessary and other components are uniformly mixed.
Among them, the triepoxy compound (A-1) used in the present invention exhibits a solid state at room temperature and is difficult to mix with other components as it is. Therefore, in preparing the resin composition for optical three-dimensional modeling of the present invention. The following method is preferably employed.
That is, all the cationically polymerizable organic compounds (A) including the triepoxy compound (A-1) are mixed in a liquid state under heating (heating temperature of about 90 to 110 ° C.), and then the mixture is brought to room temperature. Return, mix the radical polymerizable organic compound (B), the cationic polymerization initiator (C), the radical polymerization initiator (D) and other components as necessary to the mixture at room temperature to form a liquid at room temperature. A method of preparing the present resin composition for optical three-dimensional modeling of the present invention is preferably employed.

  When the nano-silica particles (E) are contained in the optical three-dimensional modeling resin composition of the present invention, the nano-silica particles (E) can be uniformly mixed and dispersed in the optical three-dimensional modeling resin composition. For example, the nano-silica particles (E) or the dispersion containing the nano-silica particles (E) may be a cationic polymerizable organic compound (A), a radical polymerizable organic compound (B), a cation A method of later mixing the nanosilica particles (E) or the nanosilica particle (E) dispersion in the resin composition for optical three-dimensional modeling prepared by mixing the polymerization initiator (C) and the radical polymerization initiator (D), One or both of the cationically polymerizable organic compound (A) and the radically polymerizable organic compound (B) was preliminarily mixed with the nanosilica particles (E) or the nanosilica particle (E) dispersion. In, and a method of mixing the other ingredients and the like. When preparing the resin composition for optical three-dimensional model | molding of this invention containing a nano silica particle using the dispersion in which the nano silica particle (E) was disperse | distributed in a cationically polymerizable organic compound, dispersion | distribution of the said nano silica particle (E) When the resin composition for optical three-dimensional modeling of the present invention is prepared after the product is previously mixed in the cationic polymerizable organic compound (A), the optical three-dimensional modeling in which the nanosilica particles (E) are uniformly dispersed is prepared. Resin composition can be obtained.

Any of the conventionally known optical three-dimensional modeling methods and apparatuses can be used for optical three-dimensional modeling using the resin composition for optical three-dimensional modeling 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 three-dimensional structure obtained by performing the optical three-dimensional modeling using the resin composition for optical three-dimensional modeling of the present invention may be used as it is without performing post-curing treatment or heat treatment. It is preferably used after post-curing treatment and / or heat treatment. At that time, the post-curing treatment by irradiation with ultraviolet rays can be performed by adopting the same methods and conditions as conventionally employed in the field of optical three-dimensional modeling. Also, heat treatment can be performed by using the same methods and conditions as conventionally employed in the field of optical three-dimensional modeling, and in particular, when heat treatment is performed using a step heating method, distortion and deformation are performed. It is possible to obtain a three-dimensionally shaped object having no appearance and excellent physical properties. The step heating method is not limited. For example, after gradually heating to 80 ° C. and reaching 80 ° C., heating is performed at the same temperature for a predetermined time, and then further gradually heating to 100 ° C. to 100 ° C. And the like, followed by heating at the same temperature for a predetermined time, then further gradually heating to 120 ° C. and reaching 120 ° C., followed by heating at the same temperature for a predetermined time.

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

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the examples. In the following examples, “parts” means parts by mass.
In addition, in the following examples, the average particle diameter of the nano silica particles, the viscosity of the resin composition for optical three-dimensional modeling, the specific gravity, and the mechanical characteristics of the three-dimensional model obtained by optical modeling [tensile characteristics (tensile strength (tensile breaking strength, tensile strength) (Measurement of elongation at break, tensile modulus), bending properties (bending strength, flexural modulus)], heat distortion temperature, total light transmittance and yellowness were measured or calculated as follows.

(1) Average particle diameter of nano silica particles:
Measurements were made by neutron small angle scattering (SANS). The small-angle neutron scattering method (SANS) is a method for measuring the structure of a nanoscale substance, which is difficult to measure by an electron microscope or a small-angle X-ray scattering method, using small-angle scattering of neutrons having a large transmission power.

(2) Viscosity of the resin composition for optical three-dimensional modeling:
After the resin composition for optical three-dimensional modeling is put in a thermostatic bath at 25 ° C. and the temperature of the resin composition for optical three-dimensional modeling is adjusted to 25 ° C., a B-type viscometer (manufactured by Toki Sangyo Co., Ltd.) is used. And measured at a rotational speed of 20 rpm.

(3) Specific gravity of the resin composition for optical three-dimensional modeling:
Using a Geryusack type specific gravity bottle (manufactured by Tokyo Glass Instrument Co., Ltd., 50 mL), measurement was performed with an electronic balance (measurement temperature 25 ° C.).

(4) Tensile properties of the three-dimensional structure (tensile breaking strength, tensile breaking elongation, tensile elastic modulus):
Using a high-pressure mercury lamp for a three-dimensional modeled object (a dumbbell-shaped test piece based on JIS K-7113) (three-dimensional modeled object after post-curing treatment) obtained by optical three-dimensional modeling in the following examples or comparative examples After curing by irradiation with ultraviolet rays (irradiation at 3 mW / cm ² for 20 minutes) at room temperature (25 ° C.), heating at 60 ° C. for 2 hours and further curing after heating (Examples 1 to 5) And Comparative Examples 1 to 3), or those heated at 120 ° C. for 2 hours and further cured after heating (Example 5), according to JIS K-7113, the tensile breaking strength (tensile strength) of the test piece, The tensile elongation at break (tensile elongation) and the tensile modulus were measured.

(5) Bending properties (bending strength, bending elastic modulus) of the three-dimensional structure:
A three-dimensional model obtained by optical three-dimensional modeling in the following examples or comparative examples (a bar-shaped test piece according to JIS K-7171) (three-dimensional model before post-curing treatment) at room temperature (25 ° C. ) Is irradiated with ultraviolet rays using a high-pressure mercury lamp (irradiated at 3 mW / cm ² for 20 minutes), post-cured, then heated at 60 ° C. for 2 hours and further heated and cured (Examples 1 to 5) And Comparative Examples 1 to 3), or those heated at 120 ° C. for 2 hours and further cured after heating (Example 5), according to JIS K-7171, the bending strength and bending elastic modulus of the test piece were measured. did.

(6) Thermal deformation temperature of the three-dimensional structure:
A three-dimensional model obtained by optical three-dimensional modeling in the following examples or comparative examples (a bar-shaped test piece according to JIS K-7171) (three-dimensional model before post-curing treatment) at room temperature (25 ° C. ) Is irradiated with ultraviolet rays using a high-pressure mercury lamp (irradiated at 3 mW / cm ² for 20 minutes), post-cured, then heated at 60 ° C. for 2 hours and further heated and cured (Examples 1 to 6). And Comparative Examples 1 to 3) or a sample cured by heating at 120 ° C. for 2 hours and further cured after heating (Example 5), using “HDT Tester 6M-2” manufactured by Toyo Seiki Co., Ltd. In accordance with JIS K-7207 (Method A) (high load) for applying a load of 1.81 MPa to JIS K-7207 (Method B) (low load) for applying a load of 0.45 MPa to the test piece The heat distortion temperature of was measured.

(7) Total light transmittance of the three-dimensional structure:
Three-dimensional modeled object (length × width × thickness = 45 mm × 20 mm × 5 mm) (three-dimensional modeled object before post-curing treatment) obtained by optical modeling in the following examples or comparative examples at room temperature (25 ° C.) After UV curing using a high pressure mercury lamp (irradiation at 3 mW / cm ² for 20 minutes) followed by curing, 60 ° C. for 2 hours, 80 ° C. for 2 hours, 100 ° C. for 2 hours or 120 ° C. for 2 hours. Heat treatment is performed using the heat treatment conditions (in Example 1 and Example 5, a heat treatment test at 140 ° C. for 2 hours is also performed), and total light transmission in the thickness direction of the three-dimensional structure after each heat treatment The rate (%) was measured.
The total light transmittance was obtained by measuring the double beam standard illuminant D65 spectral transmittance using an ultraviolet-visible spectrophotometer “UV-39001” manufactured by Hitachi High-Technology Corporation.

(8) Yellowness of the three-dimensional structure:
Using a high-pressure mercury lamp at room temperature (25 ° C.) in a three-dimensional model (length × width × thickness = 45 mm × 20 mm × 5 mm) (three-dimensional model before post-curing treatment) prepared in the following examples or comparative examples After heat curing with UV irradiation (irradiation at 3 mW / cm ² for 20 minutes), heat treatment conditions of 60 ° C. for 2 hours, 80 ° C. for 2 hours, 100 ° C. for 2 hours or 120 ° C. for 2 hours are adopted. (In Example 1 and Example 5, a heat treatment test at 140 ° C. for 2 hours was also carried out), and the yellowness in the thickness direction of the three-dimensional structure after each heat treatment was measured.
The yellowness was measured by obtaining a yellow index (YI) defined in JIS K7373 by color analysis using an ultraviolet-visible spectrophotometer “UV-39001” manufactured by Hitachi High-Technology Corporation. .

Example 1
(1) Triepoxy compound (A-1) [2- (4-glycidyloxyphenyl) -2- [4- [1,1-bis (4-glycidyloxyphenyl) ethyl] phenyl] propane] (Purin Corporation "Techmore VG3101L" manufactured by Tec, 20 parts, 35 parts hydrogenated bisphenol A diglycidyl ether ("HBE-100" manufactured by Shin Nippon Chemical Co., Ltd.), 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxy 2 parts of rate (“UVR-6105” manufactured by Dow Chemical Company), 15 parts of bis (3-ethyl-3-oxetanylmethyl) ether (“OXT-221” manufactured by Toagosei Co., Ltd.) and 3-ethyl-3-hydroxymethyl After heating and mixing 5 parts of oxetane (“OXT-101” manufactured by Toagosei Co., Ltd.) at about 100 ° C., The mixture was cooled to a temperature (25 ° C.), and 10 parts of dipentaerythritol pentaacrylate (“NK-A9550” manufactured by Shin-Nakamura Chemical Co., Ltd.) and lauryl acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd. “ NK-LA "), 6 parts, diphenyl [4- (phenylthio) phenyl] sulfonium hexafluoroantimonate (" CPI-101A "manufactured by San Apro) (cationic polymerization initiator) and 1-hydroxycyclohexyl phenyl ketone (Ciba A resin composition for optical three-dimensional modeling was prepared by thoroughly mixing 3 parts (total 100 parts in total) of “Irgacure 184” manufactured by Specialty Chemicals Co., Ltd. (radical polymerization initiator). When the viscosity and specific gravity of this resin composition for optical modeling were measured by the method described above, the viscosity was 632 mPa · s (25 ° C.) and the specific gravity was 1.083.

(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 100 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 Performs optical three-dimensional modeling in 2 minutes, dumbbell-shaped test piece according to JIS K-7113 for measuring physical properties, bar-shaped test piece according to JIS K-7171, solid for measuring total light transmittance A three-dimensional object for measurement of a three-dimensional object and yellowness was prepared, and its physical properties were measured by the method described above, and the results are shown in Table 1 below.
Moreover, when the measurement result of the total light transmittance and yellowness of the three-dimensional molded item obtained in Example 1 is graphed, it is shown in FIG. 1 (total light transmittance graph) and FIG. 2 (yellowness graph). It was as follows.
Further, in FIG. 3 (a), the three-dimensional structure obtained in (2) of Example 1 was irradiated with ultraviolet rays (irradiated at 3 mW / cm ² for 20 minutes) at room temperature (25 ° C.) and post-cured. A photograph of the three-dimensional structure taken (the upper photograph in FIG. 3A), and a photograph of the three-dimensional object that was further heat-treated at 120 ° C. for 2 hours [the lower photograph in FIG. Photo].

Example 2
(1) Triepoxy compound (A-1) [2- (4-glycidyloxyphenyl) -2- [4- [1,1-bis (4-glycidyloxyphenyl) ethyl] phenyl] propane] (“Techmore VG3101L ”) 10 parts, bisphenol fluorenediglycidyl ether [diepoxy compound represented by chemical formula (A-2a)] (“ Ogsol PG-100 ”manufactured by Osaka Gas Chemical Co., Ltd.), hydrogenated bisphenol A diglycidyl ether (“ HBE-100 ") 35 parts, 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate (" UVR-6105 ") 2 parts, bis (3-ethyl-3-oxetanylmethyl) ether (" OXT-221 ") 15 parts and 3-ethyl-3-hydroxymethyloxeta (“OXT-101”) 5 parts was heated to about 100 ° C. and mixed, then cooled to room temperature (25 ° C.), and dipentaerythritol pentaacrylate (“NK-A9550”) was added to the mixture at room temperature. 10 parts, 6 parts of lauryl acrylate (“NK-LA”), 4 parts of diphenyl [4- (phenylthio) phenyl] sulfonium hexafluoroantimonate (“CPI-101A”) (cationic polymerization initiator) and 1-hydroxycyclohexylphenyl A resin composition for optical three-dimensional modeling was prepared by thoroughly mixing 3 parts of ketone (“Irgacure 184”) (radical polymerization initiator) (total 100 parts in total). When the viscosity and specific gravity of this resin composition for optical modeling were measured by the method described above, the viscosity was 680 mPa · s (25 ° C.) and the specific gravity was 1.099.
(2) Using the resin composition for optical three-dimensional modeling obtained in (1) above, optical three-dimensional modeling is performed in the same manner as (2) of Example 1, and JIS K-7113 for measuring physical properties is performed. A dumbbell-shaped specimen conforming to JIS, a bar-shaped specimen conforming to JIS K-7171, a three-dimensional molded article for measuring the total light transmittance, and a three-dimensional molded article for measuring yellowness are prepared, and the physical properties thereof are measured. Measurement was performed by the method described above. The results are shown in Table 1 below.

Example 3
(1) Triepoxy compound (A-1) [2- (4-glycidyloxyphenyl) -2- [4- [1,1-bis (4-glycidyloxyphenyl) ethyl] phenyl] propane] (“Techmore VG3101L ”) 30 parts, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate (“ UVR-6105 ”) 27 parts, bis (3-ethyl-3-oxetanylmethyl) ether (“ OXT-221 ”) ”) And 15 parts of 3-ethyl-3-hydroxymethyloxetane (“ OXT-101 ”) were heated to about 100 ° C. and mixed, then cooled to room temperature (25 ° C.) and the mixture was allowed to cool to room temperature. 10 parts of dipentaerythritol pentaacrylate (“NK-A9550”), 6 parts of lauryl acrylate (“NK-LA”), 4 parts of phenyl [4- (phenylthio) phenyl] sulfonium hexafluoroantimonate (“CPI-101A”) (cationic polymerization initiator) and 3 parts of 1-hydroxycyclohexyl phenyl ketone (“Irgacure 184”) (radical polymerization initiator) (Total 100 parts in total) was mixed well to prepare a resin composition for optical three-dimensional modeling. When the viscosity and specific gravity of this resin composition for optical modeling were measured by the method described above, the viscosity was 588 mPa · s (25 ° C.) and the specific gravity was 1.119.
(2) Using the resin composition for optical three-dimensional modeling obtained in (1) above, optical three-dimensional modeling is performed in the same manner as (2) of Example 1, and JIS K-7113 for measuring physical properties is performed. A dumbbell-shaped specimen conforming to JIS, a bar-shaped specimen conforming to JIS K-7171, a three-dimensional molded article for measuring the total light transmittance, and a three-dimensional molded article for measuring yellowness are prepared, and the physical properties thereof are measured. Measurement was performed by the method described above. The results are shown in Table 1 below.

Example 4
(1) Triepoxy compound (A-1) [2- (4-glycidyloxyphenyl) -2- [4- [1,1-bis (4-glycidyloxyphenyl) ethyl] phenyl] propane] (“Techmore VG3101L ”) 20 parts, hydrogenated bisphenol A diglycidyl ether (“ HBE-100 ”) 15 parts, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate (“ UVR-6105 ”) 2 parts, A dispersion of 15 parts of bis (3-ethyl-3-oxetanylmethyl) ether ("OXT-221"), 5 parts of 3-ethyl-3-hydroxymethyloxetane ("OXT-101") and nano silica particles (manufactured by Nano Resin Co., Ltd.) “Nanopox A 610”, nanosilica particles having an average particle size of about 20 nm are cyclic aliphatic epoxy resins After mixing 20 parts of the dispersion dispersed in nano-silica particles (content of 40% by mass) at about 100 ° C., the mixture was cooled to room temperature (25 ° C.), and dipentaerythritol pentane was added to the mixture at room temperature. 10 parts of acrylate ("NK-A9550"), 6 parts of lauryl acrylate ("NK-LA"), 4 parts of diphenyl [4- (phenylthio) phenyl] sulfonium hexafluoroantimonate ("CPI-101A") Agent) and 1 part of 1-hydroxycyclohexyl phenyl ketone ("Irgacure 184") (radical polymerization initiator) (total 100 parts in total) were mixed well to prepare a resin composition for optical three-dimensional modeling (optical solid) The content of nano silica particles in the resin composition for modeling is 8% by mass). When the viscosity and specific gravity of this resin composition for optical modeling were measured by the method described above, the viscosity was 656 mPa · s (25 ° C.) and the specific gravity was 1.143.
(2) Using the resin composition for optical three-dimensional modeling obtained in (1) above, optical three-dimensional modeling is performed in the same manner as (2) of Example 1, and JIS K-7113 for measuring physical properties is performed. A dumbbell-shaped specimen conforming to JIS, a bar-shaped specimen conforming to JIS K-7171, a three-dimensional molded article for measuring the total light transmittance, and a three-dimensional molded article for measuring yellowness are prepared, and the physical properties thereof are measured. Measurement was performed by the method described above. The results are shown in Table 1 below.

Example 5
(1) Triepoxy compound (A-1) [2- (4-glycidyloxyphenyl) -2- [4- [1,1-bis (4-glycidyloxyphenyl) ethyl] phenyl] propane] (“Techmore VG3101L ”) 20 parts, hydrogenated bisphenol A diglycidyl ether (“ HBE-100 ”) 5 parts, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate (“ UVR-6105 ”) 2 parts, A dispersion of 15 parts of bis (3-ethyl-3-oxetanylmethyl) ether ("OXT-221"), 5 parts of 3-ethyl-3-hydroxymethyloxetane ("OXT-101") and nano silica particles (manufactured by Nano Resin Co., Ltd.) “Nanopox A 610”, nanosilica particles having an average particle diameter of about 20 nm in the cycloaliphatic epoxy resin 30 parts of the dispersed dispersion and the content of nanosilica particles (40% by mass) were heated and mixed at about 100 ° C., then cooled to room temperature (25 ° C.), and the mixture was dipentaerythritol pentaacrylate at room temperature. ("NK-A9550") 10 parts, lauryl acrylate ("NK-LA") 6 parts, diphenyl [4- (phenylthio) phenyl] sulfonium hexafluoroantimonate ("CPI-101A") 4 parts (cationic polymerization initiator) ) And 1-hydroxycyclohexyl phenyl ketone (“Irgacure 184”) (radical polymerization initiator) 3 parts (total 100 parts in total) were mixed well to prepare a resin composition for optical three-dimensional modeling (optical three-dimensional modeling) The content of nano silica particles in the resin composition for use is 12 mass%). When the viscosity and specific gravity of this resin composition for optical modeling were measured by the method described above, the viscosity was 680 mPa · s (25 ° C.) and the specific gravity was 1.175.
(2) Using the resin composition for optical three-dimensional modeling obtained in (1) above, optical three-dimensional modeling is performed in the same manner as (2) of Example 1, and JIS K-7113 for measuring physical properties is performed. A dumbbell-shaped specimen conforming to JIS, a bar-shaped specimen conforming to JIS K-7171, a three-dimensional molded article for measuring the total light transmittance, and a three-dimensional molded article for measuring yellowness are prepared, and the physical properties thereof are measured. Measurement was performed by the method described above. The results are shown in Table 1 below.
Moreover, when the measurement result of the total light transmittance and yellowness of the three-dimensional molded item obtained in Example 5 is graphed, it is shown in FIG. 1 (total light transmittance graph) and FIG. 2 (yellowness graph). It was as follows.
Further, in FIG. 3 (b), the three-dimensional structure obtained in (2) of Example 5 was irradiated with ultraviolet rays (irradiated at 3 mW / cm ² for 20 minutes) at room temperature (25 ° C.) and post-cured. A photograph of the three-dimensional structure taken (the upper photograph in FIG. 3B), and a photograph of the three-dimensional object that was further heat-treated at 140 ° C. for 2 hours [the lower photograph in FIG. 3B. Photo].

<< Comparative Example 1 >>
(1) 55 parts hydrogenated bisphenol A diglycidyl ether (“HBE-100”), 2 parts 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate (“UVR-6105”), bis ( 15 parts of 3-ethyl-3-oxetanylmethyl) ether (“OXT-221”), 5 parts of 3-ethyl-3-hydroxymethyloxetane (“OXT-101”), dipentaerythritol pentaacrylate (“NK-A9550”) ) 10 parts, lauryl acrylate (“NK-LA”) 6 parts, diphenyl [4- (phenylthio) phenyl] sulfonium hexafluoroantimonate (“CPI-101A”) 4 parts (cationic polymerization initiator) and 1-hydroxycyclohexyl Phenyl ketone ("Irgacure 184" It was prepared (radical polymerization initiator) 3 parts for stereolithography resin composition was mixed well at room temperature (the total 100 parts total). When the viscosity and specific gravity of this resin composition for optical modeling were measured by the method described above, the viscosity was 204 mPa · s (25 ° C.) and the specific gravity was 1.071.
(2) Using the resin composition for optical three-dimensional modeling obtained in (1) above, optical three-dimensional modeling is performed in the same manner as (2) of Example 1, and JIS K-7113 for measuring physical properties is performed. A dumbbell-shaped specimen conforming to JIS, a bar-shaped specimen conforming to JIS K-7171, a three-dimensional molded article for measuring the total light transmittance, and a three-dimensional molded article for measuring yellowness are prepared, and the physical properties thereof are measured. Measurement was performed by the method described above. The results are shown in Table 2 below.
Moreover, when the measurement result of the total light transmittance and yellowness of the three-dimensional model | molding obtained in this comparative example 1 is made into a graph, it shows in FIG. 1 (graph of total light transmittance) and FIG. 2 (graph of yellowness). It was as follows.
Further, in FIG. 3C, the three-dimensional structure obtained in (2) of Comparative Example 1 was irradiated with ultraviolet rays (irradiated at 3 mW / cm ² for 20 minutes) at room temperature (25 ° C.) and post-cured. A photograph of the three-dimensional structure taken (the upper photograph of FIG. 3C), and a photograph of the three-dimensional object that was further heat-treated at 120 ° C. for 2 hours [the lower photograph of FIG. Photo].

<< Comparative Example 2 >>
(1) 35 parts hydrogenated bisphenol A diglycidyl ether (“HBE-100”), 2 parts 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate (“UVR-6105”), bisphenol A 20 parts of diglycidyl ether ("EP-4100E" manufactured by Adeka), 15 parts of bis (3-ethyl-3-oxetanylmethyl) ether ("OXT-221") and 3-ethyl-3-hydroxymethyloxetane ("OXT") -101 ") 5 parts heated to about 100 <0> C and mixed, then cooled to room temperature (25 <0> C), and to the mixture 10 parts dipentaerythritol pentaacrylate (" NK-A9550 ") at room temperature, 6 parts lauryl acrylate ("NK-LA"), diphenyl [4- (phenylthio) phenyl] 4 parts of rufonium hexafluoroantimonate (“CPI-101A”) (cationic polymerization initiator) and 3 parts of 1-hydroxycyclohexyl phenyl ketone (“Irgacure 184”) (radical polymerization initiator) (100 parts in total) The resin composition for optical three-dimensional modeling was prepared by mixing well. When the viscosity and specific gravity of this resin composition for optical modeling were measured by the method described above, the viscosity was 276 mPa · s (25 ° C.) and the specific gravity was 1.089.
(2) Using the resin composition for optical three-dimensional modeling obtained in (1) above, optical three-dimensional modeling is performed in the same manner as (2) of Example 1, and JIS K-7113 for measuring physical properties is performed. A dumbbell-shaped specimen conforming to JIS, a bar-shaped specimen conforming to JIS K-7171, a three-dimensional molded article for measuring the total light transmittance, and a three-dimensional molded article for measuring yellowness are prepared, and the physical properties thereof are measured. Measurement was performed by the method described above. The results are shown in Table 2 below.

<< Comparative Example 3 >>
(1) 35 parts of hydrogenated bisphenol A diglycidyl ether (“HBE-100”), 2 parts of 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate (“UVR-6105”), orthocresol 20 parts of novolak epoxy (“N-673” manufactured by DIC Corporation), 15 parts of bis (3-ethyl-3-oxetanylmethyl) ether (“OXT-221”) and 3-ethyl-3-hydroxymethyloxetane (“ 5 parts of OXT-101 ") were heated to about 100 ° C and mixed, and then cooled to room temperature (25 ° C). To this mixture, 10 parts of dipentaerythritol pentaacrylate (" NK-A9550 "), lauryl acrylate ( "NK-LA") 6 parts, diphenyl [4- (phenylthio) phenyl] sulfoniu 4 parts of hexafluoroantimonate (“CPI-101A”) (cation polymerization initiator) and 3 parts of 1-hydroxycyclohexyl phenyl ketone (“Irgacure 184”) (radical polymerization initiator) (100 parts in total) at room temperature Were mixed well to prepare a resin composition for optical three-dimensional modeling. When the viscosity and specific gravity of this resin composition for optical modeling were measured by the method described above, the viscosity was 780 mPa · s (25 ° C.) and the specific gravity was 1.096.
(2) Using the resin composition for optical three-dimensional modeling obtained in (1) above, optical three-dimensional modeling is performed in the same manner as (2) of Example 1, and JIS K-7113 for measuring physical properties is performed. A dumbbell-shaped specimen conforming to JIS, a bar-shaped specimen conforming to JIS K-7171, a three-dimensional molded article for measuring the total light transmittance, and a three-dimensional molded article for measuring yellowness are prepared, and the physical properties thereof are measured. Measurement was performed by the method described 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 5 are cationic polymerizable organic compound (A), radical polymerizable organic compound (B), and active energy ray sensitivity. In the resin composition for optical three-dimensional modeling containing a cationic polymerization initiator (C) and an active energy ray-sensitive radical polymerization initiator (D), a triepoxy compound (A-1) is used as the cationic polymerizable organic compound (A). ) At a ratio in the range of 5 to 40% by mass based on the mass of the resin composition for optical three-dimensional modeling, it has a high heat distortion temperature and is excellent in heat resistance, Moreover, it has high tensile breaking strength and bending strength, excellent mechanical strength, moderate elongation, excellent toughness, high total light transmittance, excellent transparency, and low yellowness to hue. Excellent Cage, yet is and yellowness is also maintained high total light transmittance when exposed to high temperatures are kept small.
In particular, the resin compositions for optical three-dimensional modeling of Examples 4 and 5, which further contain nanosilica particles together with the triepoxy compound (A-1), have excellent transparency and excellent hue with little yellowing. Higher deformation temperature, excellent heat resistance, and even when exposed to an extremely high temperature of 140 ° C. for 2 hours, the decrease in total light transmittance is small and high transparency is maintained. Is excellent in heat resistance from such a point.

On the other hand, the three-dimensional object obtained from the resin composition for optical three-dimensional modeling of Comparative Examples 1 to 3 that does not contain the triepoxy compound (A-1) is the resin for optical three-dimensional modeling of Examples 1 to 5. Compared to the three-dimensional structure obtained from the composition, the heat distortion temperature is low and the heat resistance is low, and the tensile strength at break and the bending strength are low and the mechanical strength is also low.
In addition, the three-dimensional object obtained from the optical three-dimensional resin composition of Comparative Examples 1 to 3, particularly the three-dimensional object obtained from the optical three-dimensional resin composition of Comparative Examples 1 and 2, Although the total light transmittance after heating at 2 ° C. for 2 hours is high, the total light transmittance is greatly reduced after heating at 120 ° C. for 2 hours.
Furthermore, in the three-dimensional model obtained from the resin composition for optical three-dimensional modeling of Comparative Examples 1 to 3, particularly, the three-dimensional model obtained from the resin composition for optical three-dimensional modeling of Comparative Examples 1 and 2, 120 ° C. The yellowness after heating for 2 hours is high, and the hue is greatly reduced by high-temperature heating.
The results of Examples 1 to 5 and Comparative Examples 1 to 3 in Tables 1 and 2 are supported by the graphs of FIGS. 1 and 2 and the photograph of FIG.

Example 6
(1) Triepoxy compound (A-1) [2- (4-glycidyloxyphenyl) -2- [4- [1,1-bis (4-glycidyloxyphenyl) ethyl] phenyl] propane] (“Techmore VG3101L ”) 20 parts, bisphenol A diglycidyl ether (“ EP-4100E ”) 5 parts, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate (“ UVR-6105 ”) 2 parts, bis ( 15 parts of 3-ethyl-3-oxetanylmethyl) ether (“OXT-221”), 5 parts of 3-ethyl-3-hydroxymethyloxetane (“OXT-101”) and a dispersion of nanosilica particles (“Nanopox manufactured by Nanoresin Co., Ltd.) E 470 ", nanosilica particles having an average particle size of about 20 nm are bisphenol A diglycidyl ester 30 parts of a dispersion dispersed in tellurium and the content of nanosilica particles (40% by mass) were mixed by heating at about 100 ° C., and then cooled to room temperature (25 ° C.). 10 parts erythritol pentaacrylate (“NK-A9550”), 6 parts lauryl acrylate (“NK-LA”), 4 parts diphenyl [4- (phenylthio) phenyl] sulfonium hexafluoroantimonate (“CPI-101A”) (cation) Polymerization initiator) and 1 part of 1-hydroxycyclohexyl phenyl ketone (“Irgacure 184”) (radical polymerization initiator) (total 100 parts in total) were mixed well to prepare a resin composition for optical three-dimensional modeling (optical) 15% by mass of nanosilica particles in the three-dimensional resin composition. When the viscosity of this resin composition for optical modeling was measured by the method described above, the viscosity was 750 mPa · s (25 ° C.).
(2) Using the resin composition for optical three-dimensional modeling obtained in (1) above, optical three-dimensional modeling is performed in the same manner as (2) of Example 1, and JIS K-7171 for measuring physical properties is performed. A bar-shaped test piece conforming to the above was prepared, and its thermal deformation temperature was measured. The thermal deformation temperature by Method A (load 1.81 MPa) was 70 ° C., and the thermal deformation temperature by Method B (load 0.45 MPa) was It was 85 ° C.

  The resin composition for optical three-dimensional model | molding of this invention which contains at least 1 sort (s) of a triepoxy compound (A-1) in the quantity prescribed | regulated by this invention has high curing sensitivity by an active energy ray, and is low. Viscosity is excellent in handling during modeling, not only has excellent properties such as high resolution of modeling objects, excellent modeling accuracy, and low volumetric shrinkage during curing, but also has high heat distortion temperature and excellent heat resistance. Moreover, it has a high tensile strength and bending strength, has excellent mechanical strength, has a moderate elongation, has excellent toughness, and has a three-dimensional structure that has excellent transparency and hue. Therefore, using the resin composition for optical three-dimensional modeling of the present invention, for precision parts, electrical / electronic parts, furniture, building structures, automotive parts, various containers, castings, molds, mother dies, etc. Models and models for machining, parts for designing complex heat medium circuits, parts for analyzing and planning heat medium behavior of complex structures, and other various three-dimensional objects with complex physical properties that have complex shapes and structures It can be obtained smoothly with high modeling speed and dimensional accuracy.

Claims (5)

<< i >> Based on the total mass of the resin composition for optical three-dimensional modeling, the cationic polymerizable organic compound (A) is 30 to 85 mass% , the radical polymerizable organic compound (B) is 10 to 60 mass% , and the active energy. A resin composition for optical three-dimensional modeling containing 0.1 to 10% by mass of a line-sensitive cationic polymerization initiator (C) and 0.1 to 10% by mass of an active energy ray-sensitive radical polymerization initiator (D). Because;
<< ii >> As the cationically polymerizable organic compound (A), the following chemical formula (A-1);

A triepoxy compound (A-1) represented by the formula: 5 to 50% by mass based on the mass of the resin composition for optical three-dimensional modeling ;
<< iii >> As part of the cationically polymerizable organic compound (A), the epoxy compound (A-3) having a cycloalkene oxide structure in the molecule is 80% by mass based on the mass of the cationically polymerizable organic compound (A). In the following proportions;
<< iv >> As a part of the cationically polymerizable organic compound (A), an oxetane compound (A-4) having one or more oxetane groups is selected from 5 to 5 based on the mass of the cationically polymerizable organic compound (A). In a proportion of 50% by weight; and
<< v >> As the radical polymerizable organic compound (B), a compound having two or more (meth) acryl groups is contained in a proportion of 50% by mass or more based on the mass of the radical polymerizable organic compound (B);
A resin composition for optical three-dimensional modeling characterized by the above. The nanosilica particles having an average particle size of 1 to 200 nm (E), for stereolithography of claim 1, further comprising in an amount of 1 to 50% by weight based on the total weight of stereolithography resin composition Resin composition. As a part of the cationically polymerizable organic compound (A), the following general formula (A-2);

(In the formula, m represents an integer of 0 to 10.)
The resin for optical three-dimensional model | molding of Claim 1 or 2 which contains the diepoxy compound (A-2) represented by these by the ratio of 20 mass% or less based on the total mass of the resin composition for optical three-dimensional model | molding. Composition. The manufacturing method of the three-dimensional molded item characterized by performing an optical three-dimensional model | molding using the resin composition for optical three-dimensional model | molding of any one of Claims 1-3 . Performing optical three-dimensional modeling using the optical three-dimensional model according to any one of claims 1 to 3 to create a three-dimensional model, and subjecting the three-dimensional model to ultraviolet irradiation treatment and / or heat treatment. The manufacturing method of the three-dimensional molded item to be characterized.

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