JP2009203306A - Resin composition for optical three-dimensional shaping - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition for an optical shaped article, which produces a three-dimensional shaped article having high photocuring sensitivity, a low coefficient of moisture absorption, an excellent storage stability, a short shaping time, excellent dimensional stability, durability, water resistance, moisture resistance and kinetic property in good productivity. <P>SOLUTION: The resin composition for an optical three-dimensional shaped article comprises an alicyclic diglycidyl ether compound represented by general formula (I) (wherein R<SP>1</SP>is a hydrogenated bisphenol A residue, a hydrogenated bisphenol F residue, a hydrogenated bisphenol Z residue, a cyclohexanedimethanol residue or a tricyclodecanedimethanol residue), a polyoxetane compound and a monooxetane compound as cationically polymerizable organic compounds, a di(meth)acrylate compound and a poly(meth)acrylate compound as radically polymerizable organic compounds and an antimony aromatic sulfonium compound represented by formula: [S<SP>+</SP>(R<SP>2</SP>)<SB>a</SB>(R<SP>3</SP>)<SB>b</SB>(R<SP>4</SP>)<SB>c</SB>][Sb<SP>-</SP>F<SB>6</SB>]m as a cationic polymerization initiator but not an ester carbonyl group-containing cationically polymerizable organic compound. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a resin composition for optical three-dimensional modeling and a method for producing an optical three-dimensional model using the composition. More specifically, the present invention has high photocuring sensitivity and low absorption of moisture and moisture before and after photocuring, dimensional accuracy, modeling accuracy, dimensional stability, water resistance, moisture resistance, Three-dimensional modeling using a resin composition for optical three-dimensional modeling and an optical three-dimensional modeling resin composition capable of producing an optical three-dimensional model excellent in toughness and other mechanical properties at high modeling speed with high productivity A method for manufacturing a product is provided.

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 a computer-controlled ultraviolet ray so that a desired pattern is obtained on the liquid surface of the liquid photocurable resin placed in a container. Finally, a one-layer liquid resin is supplied onto the cured layer, and similarly cured by irradiation with ultraviolet rays in the same manner as described above, and finally a three-dimensional structure is obtained by repeating the lamination operation to obtain a continuous cured layer. The method of obtaining 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 with active energy rays, low viscosity and excellent handling at the time of molding, and less absorption of moisture and moisture over time, lowering of curing sensitivity There is no problem, the resolution of the molded object is high and the modeling accuracy is excellent, the volumetric shrinkage ratio at the time of curing is small, and the molded object obtained by curing has mechanical properties, durability, water resistance, moisture resistance, heat resistance Various characteristics such as excellent properties are required.

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

Among the above, in a photocurable resin composition containing a cationically polymerizable organic compound such as an epoxy compound, a photocationic polymerization initiator present in the system generates a cationic species (H ⁺ ) by light irradiation, It is related to the cationically polymerizable organic compound in a chain, the cationically polymerizable organic compound is opened and the reaction proceeds. When a photocurable resin composition based on a cationically polymerizable organic compound such as an epoxy compound is used, it is generally obtained as compared with a case where a photocurable resin composition based on a radical polymerizable organic compound is used. A molded article having a small shrinkage ratio of the photocured product and excellent in dimensional stability and dimensional accuracy can be obtained.

  The cationic photopolymerization initiator for photopolymerizing the cationically polymerizable organic compound is composed of an aromatic sulfonium salt of a group 16 element, an aromatic onium salt of a group 17 element, an aromatic onium salt of a group 15 element, or the like. Photocationic polymerization initiators are known (see Patent Documents 1 to 8, etc.). Among them, in the photocurable resin composition containing a cationically polymerizable organic compound, a sulfonium salt containing antimony is widely used as a photocationic polymerization initiator from the viewpoint of the reactivity of the photocurable resin composition.

In the resin composition for optical three-dimensional modeling using antimony sulfonium salt as a photocationic polymerization initiator, 3,4-epoxycyclohexylmethyl is used as at least a part of the cationically polymerizable organic compound in order to increase the photocuring rate. -3 ′, 4′-epoxycyclohexanecarboxylate and other cationically polymerizable organic compounds having an ester carbonyl group in the molecule are generally used, and when the cationically polymerizable organic compound is not included, the photocuring rate Becomes slower.
However, since a cationically polymerizable organic compound having an ester carbonyl group in the molecule has high water absorption and hygroscopicity, the resin composition for optical three-dimensional modeling containing the cationic polymerizable organic compound and photocuring the resin composition. All of the three-dimensional objects obtained by this method have high water absorption and hygroscopicity, and it is necessary to strictly manage to prevent moisture absorption during storage of the optical three-dimensional resin composition before photocuring. In addition, the three-dimensional structure obtained by photocuring is likely to be deformed by moisture absorption, reduced in dimensional accuracy or reduced in strength, and has low shrinkage and dimensional stability due to the use of a cationically polymerizable organic compound. The actual situation is that the advantage of dimensional accuracy cannot be fully exhibited.
In addition, along with the expansion of applications of stereolithography, in combination with the characteristics of heat resistance, moisture resistance, dimensional accuracy, dimensional stability, it has excellent toughness and is not easily damaged even when external stress such as bending is applied. There is a demand for a resin composition for optical three-dimensional modeling that can form a three-dimensional model having excellent durability.

Japanese Examined Patent Publication No. 7-103218 Japanese Examined Patent Publication No. 52-14277 Japanese Patent Publication No.52-14278 Japanese Patent Publication No.52-14279 JP 2002-241363 A JP 2001-81096 A JP 2007-262401 A Japanese Patent Laid-Open No. 2007-238828 Paul F. Jacobs, “Rapid Prototyping & Manufacturing, Fundamentals of Stereo-Lithography”, “Society of Manufacturing Engineers”, 1992, p. 28-39.

It is an object of the present invention to produce a shaped article with high productivity in a shortened active energy ray irradiation time with high photocuring sensitivity, which contains a conventional antimony sulfonium salt as a cationic polymerization initiator. Optics that absorb less moisture and moisture before and after photocuring, and have excellent storage stability, handleability, and dimensional stability and dimensional accuracy of three-dimensional objects obtained by stereolithography It is providing the resin composition for three-dimensional modeling.
The object of the present invention is to form a three-dimensional structure that is excellent in toughness, is not damaged even when external stress such as impact and bending is applied, has excellent durability, and is excellent in other mechanical properties. It is providing the resin composition for optical three-dimensional modeling which can do.

As a result of intensive studies by the present inventors to solve the above problems, an optical system 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 Cation-polymerizable organic compound having an ester carbonyl group as the cationically polymerizable organic compound in the use of the antimony sulfonium salt that has been widely used as an active energy ray-sensitive cationic polymerization initiator Di (meth) acrylate compounds and (meth) having two (meth) acryloyloxy groups as radically polymerizable organic compounds and using specific alicyclic diepoxy compounds, polyoxetane compounds and monooxetane compounds without using Acryloyloxy When a poly (meth) acrylate compound having 3 or more is used, a resin composition for optical three-dimensional modeling with high photocuring sensitivity can be obtained, and the three-dimensional molded product obtained from the resin composition for optical three-dimensional modeling Found that even when left under high humidity, the absorption of moisture is small, the storage stability and the dimensional stability over time are excellent, and the desired optically shaped article can be produced with high dimensional accuracy.
Furthermore, the present inventors have found that the three-dimensional structure obtained from the above-described resin composition for optical three-dimensional structure is excellent in toughness and does not break even when external stress such as impact or bending is applied, and is durable. In addition, the present inventors have found that it is excellent in other characteristics such as mechanical properties, water resistance and heat resistance, and has completed the present invention based on these 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 general formula (I):

（式中、R¹は、水素添加ビスフェノールＡ残基、水素添加ビスフェノール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またはトリシクロデカンジメタノール残基を示す。）
で表される脂環式ジグリシジルエーテル化合物（Ｉ）；
・オキセタン基を２個以上有するポリオキセタン化合物（ＯＸｐ）；および、
・オキセタン基を１個有するモノオキセタン化合物（ＯＸｍ）；
を含有し；
（iii） ラジカル重合性有機化合物（Ｂ）として、
・（メタ）アクリロイルオキシ基を２個有するジ（メタ）アクリレート化合物（Ｂ１）；および、
・（メタ）アクリロイルオキシ基を３個以上有するポリ（メタ）アクリレート化合物（Ｂ２）；
を含有し；
（iv） 活性エネルギー線感受性カチオン重合開始剤（Ｃ）が、下記の一般式（II）；

(In the formula, R ¹ represents a hydrogenated bisphenol A residue, a hydrogenated bisphenol F residue, a hydrogenated bisphenol Z residue, a cyclohexanedimethanol residue or a tricyclodecanedimethanol residue.)
An alicyclic diglycidyl ether compound (I) represented by:
A polyoxetane compound (OXp) having two or more oxetane groups; and
A monooxetane compound having one oxetane group (OXm);
Containing;
(Iii) As radically polymerizable organic compound (B),
A di (meth) acrylate compound (B1) having two (meth) acryloyloxy groups; and
A poly (meth) acrylate compound (B2) having 3 or more (meth) acryloyloxy groups;
Containing;
(Iv) The active energy ray-sensitive cationic polymerization initiator (C) is represented by the following general formula (II):

［上記の式（II）中、Ｒ²およびＲ³はそれぞれ独立して下記の式（ｉ）〜（iv）；

[In the above formula (II), R ² and R ³ are each independently the following formulas (i) to (iv);

｛式（ii）および式（iv）中、Ｘは塩素原子またはフッ素原子を示す｝
で表される基のいずれかであり、Ｒ⁴は下記の式（ｖ）；

{In Formula (ii) and Formula (iv), X represents a chlorine atom or a fluorine atom}
In which R ⁴ is represented by the following formula (v):

で表される基であり、ａは０〜３の整数、ｂは０〜３の整数およびｃは０または１であって、ａとｂとｃの合計が３であり、ｍは１＋ｃと同じ数である。］
で表されるアンチモンの芳香族スルホニウム化合物（II）であり；且つ、
（ｖ） 分子中にエステルカルボニル基を有するカチオン重合性有機化合物を実質的に含有しない；
ことを特徴とする光学的立体造形用樹脂組成物である。

A is an integer of 0 to 3, b is an integer of 0 to 3, and c is 0 or 1, and the sum of a, b and c is 3, and m is the same as 1 + c. Is a number. ]
An aromatic sulfonium compound (II) of antimony represented by:
(V) substantially free of a cationically polymerizable organic compound having an ester carbonyl group in the molecule;
The resin composition for optical three-dimensional modeling characterized by the above-mentioned.

And this invention,
(2) The content ratio of the cationically polymerizable organic compound (A): radically polymerizable organic compound (B) is 30:70 to 90:10, and the antimony aromatic sulfonium compound (II) is cationically polymerizable. It contains in the ratio of 0.1-10 mass% based on the mass of an organic compound (A), and an active energy ray sensitive radical polymerization initiator (D) is 0. 0 based on the mass of a radically polymerizable organic compound (B). The resin composition for optical three-dimensional modeling according to (1), which is contained at a ratio of 1 to 20% by mass;
(3) The optical system according to (1) or (2) above, which contains the alicyclic diglycidyl ether compound (I) in a proportion of 20 to 95% by mass based on the total mass of the cationically polymerizable organic compound (A). Resin composition for three-dimensional modeling;
(4) Based on the total mass of the cationically polymerizable organic compound (A), the polyoxetane compound (OXp) is contained in a proportion of 5 to 50% by mass and the monooxetane compound (OXm) in a proportion of 2 to 40% by mass ( The resin composition for optical three-dimensional modeling according to any one of 1) to (3);
(5) The total content of the alicyclic diglycidyl ether compound (I), the polyoxetane compound (OXp) and the monooxetane compound (OXm) based on the total mass of the cationically polymerizable organic compound (A) is 40 to 100% by mass. The resin composition for optical three-dimensional modeling according to any one of (1) to (4), and
(6) Based on the total mass of the radical polymerizable organic compound (B), the di (meth) acrylate compound (B1) is 20 to 60% by mass and the poly (meth) acrylate compound (B2) is 30 to 70% by mass. The resin composition for optical three-dimensional modeling according to any one of (1) to (5), which is contained in a proportion;
It is.

Furthermore, the present invention provides
(7) The polyoxetane compound (OXp) is represented by the following general formula (III-1);

（式中、２個のＲ⁵は互いに同じかまたは異なる炭素数１〜５のアルキル基、Ｒ⁶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、ｐは０または１を示す。）
で表されるジオキセタン化合物である請求項１〜６のいずれか１項に記載の光学的立体造形用樹脂組成物；および、
（８） モノオキセタン化合物（ＯＸｍ）が、下記の一般式（III−２ａ）で表されるモノオキセタン化合物（III−２ａ）および下記の一般式（III−２ｂ）で表されるモノオキセタン化合物（III−２ｂ）から選ばれる少なくとも１種のモノオキセタン化合物である、前記（１）〜（７）のいずれかの光学的立体造形用樹脂組成物である。

Wherein two R ⁵ are the same or different alkyl groups having 1 to 5 carbon atoms, R ⁶ is a divalent organic group having or not having an aromatic ring, p is 0 or 1 Is shown.)
A resin composition for optical three-dimensional modeling according to any one of claims 1 to 6, which is a dioxetane compound represented by:
(8) The monooxetane compound (OXm) is a monooxetane compound (III-2a) represented by the following general formula (III-2a) and a monooxetane compound represented by the following general formula (III-2b) ( The resin composition for optical three-dimensional modeling according to any one of (1) to (7), which is at least one monooxetane compound selected from III-2b).

（式中、Ｒ⁷およびＲ⁸は炭素数１〜５のアルキル基、Ｒ⁹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、ｑは１〜６の整数を示す。）
そして、本発明は、
（９） 前記（１）〜（８）のいずれかの光学的立体造形用樹脂組成物を用いて光学的立体造形物を製造する方法である。

Wherein R ⁷ and R ⁸ are alkyl groups having 1 to 5 carbon atoms, R ⁹ is an alkylene group having 2 to 10 carbon atoms which may have an ether bond, and q is an integer of 1 to 6. )
And this invention,
(9) A method for producing an optical three-dimensional object using the resin composition for optical three-dimensional object modeling according to any one of (1) to (8).

The resin composition for optical three-dimensional modeling of the present invention using an antimony aromatic sulfonium compound as the cationic polymerizable organic compound (hereinafter referred to as “resin composition for optical modeling”) is a cationic polymerizable organic having an ester carbonyl group. It does not contain a compound, has high curing sensitivity by active energy rays, and can produce a desired three-dimensional modeled object with high productivity in a shortened modeling time. That is, the resin composition for optical modeling according to the present invention includes an alicyclic diglycidyl ether compound (I) having no ester carbonyl group, a polyoxetane compound (OXp), and a monooxetane compound (OXm) as a cationically polymerizable organic compound. And 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxy by containing di (meth) acrylate compound (B1) and poly (meth) acrylate compound (B2) as radically polymerizable organic compounds Despite the fact that it does not contain a highly reactive cationically polymerizable organic compound such as cyclohexanecarboxylate, the catalytic activity of the cationic polymerization initiator composed of the aromatic sulfonium compound of antimony is maintained well. Highly sensitive and highly productive with 3D modeling at high modeling speed Door can be.
Moreover, the resin composition for optical modeling of the present invention and the three-dimensional model obtained from the resin composition do not use a cationically polymerizable organic compound having an ester carbonyl group, so that the absorption of moisture and moisture is small, and the resin for optical modeling. The composition has excellent storage stability, handleability, dimensional stability and dimensional accuracy of the resulting three-dimensional structure.
Furthermore, the three-dimensional molded article obtained using the resin composition for optical modeling of the present invention is excellent in characteristics such as mechanical characteristics, water resistance, and heat resistance. In particular, by using the resin composition for optical modeling according to the present invention, a three-dimensional model that is excellent in toughness, is not easily damaged even when external stress such as impact and bending is applied, and has excellent durability. be able to.
In addition, by using the resin composition for optical modeling according to the present invention, since the moisture resistance is excellent, an effect of excellent long-term dimensional stability is obtained.

The present invention is described in detail below.
The resin composition for optical modeling of the present invention contains a cationic polymerizable organic compound (A) and a radical polymerizable organic compound (B) as an active energy ray polymerizable compound that is polymerized by irradiation with active energy rays.
As used herein, the term “active energy rays” refers to energy rays that can cure an optical modeling resin composition such as ultraviolet rays, electron beams, X-rays, radiation, and high frequencies.
The resin composition for optical modeling according to the present invention includes the following general formula (I) as the cationically polymerizable organic compound (A):

（式中、R¹は、水素添加ビスフェノールＡ残基、水素添加ビスフェノール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またはトリシクロデカンジメタノール残基を示す。）
で表される、エステルカルボニル基を持たない脂環式ジグリシジルエーテル化合物（Ｉ）を含有する。

(In the formula, R ¹ represents a hydrogenated bisphenol A residue, a hydrogenated bisphenol F residue, a hydrogenated bisphenol Z residue, a cyclohexanedimethanol residue or a tricyclodecanedimethanol residue.)
And an alicyclic diglycidyl ether compound (I) having no ester carbonyl group.

The resin composition for optical modeling according to the present invention contains a cycloaliphatic diglycidyl ether compound (I) having no ester carbonyl group as the cationic polymerizable organic compound (A), so that curing sensitivity and thick film curability are obtained. In addition, the resolution, ultraviolet transmittance, etc. are further improved, the viscosity of the resin composition for optical modeling is lowered, and modeling is performed smoothly, and the volumetric shrinkage of the optical modeled product obtained by modeling Is further reduced.
The resin composition for optical modeling of the present invention comprises an alicyclic diglycidyl ether compound (I) having no ester carbonyl group, based on the total mass of the cationically polymerizable organic compound (A), of 20 to 95% by mass. It is preferably contained in a proportion, more preferably in a proportion of 30 to 90% by mass, and still more preferably in a proportion of 50 to 90% by mass. If the content ratio of the alicyclic diglycidyl ether compound (I) is too small, the dimensional stability of the shaped article under high humidity tends to be lowered, whereas if the content ratio is too large, the photocurability tends to be lowered. .

  Specific examples of the alicyclic diglycidyl ether compound (I) having no ester carbonyl group used in the present invention include hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, and hydrogenated bisphenol Z diester. Examples thereof include glycidyl ether, cyclohexane dimethanol diglycidyl ether, and tricyclodecane dimethanol diglycidyl ether. The resin composition for optical modeling of the present invention may contain only one of the diglycidyl ethers described above as the alicyclic diglycidyl ether compound (I) having no ester carbonyl group, or 2 It may contain seeds or more. Among them, the resin composition for optical modeling according to the present invention includes a hydrogenated bisphenol A diglycidyl ether and / or tricyclodecane dimethanol diglycidyl ether as the alicyclic diglycidyl ether compound (I) having no ester carbonyl group. It is preferable from the viewpoints of availability of the alicyclic diglycidyl ether compound (I), moisture absorption resistance of the resulting molded article, and the like.

The resin composition for optical modeling according to the present invention has two or more oxetane groups in the molecule together with the alicyclic diglycidyl ether compound (I) having no ester carbonyl group as the cationic polymerizable organic compound (A). A polyoxetane compound (OXp) having a monooxetane compound (OXm) having one oxetane group in the molecule.
The resin composition for optical modeling of the present invention contains the polyoxetane compound (OXp) and the monooxetane compound (OXm), so that the photocuring sensitivity of the resin composition for optical modeling is improved, and the optical modeling product is obtained. The toughness of the steel increases, and even when stress such as impact or bending is applied, it becomes difficult to break, and durability is improved.

As the polyoxetane compound (OXp), any of a monooxetane compound having one oxetane group in one molecule and a polyoxetane compound having two or more oxetane groups in one molecule can be used.
As the polyoxetane compound (OXp), a compound having two or more oxetane groups, for example, a compound having two, three, or four oxetane groups can be used, and of these, two oxetane groups are included. Dioxetane compounds are preferably used.
In particular, as a dioxetane compound, the following general formula (III-1);

（式中、２個のＲ⁵は互いに同じかまたは異なる炭素数１〜５のアルキル基、Ｒ⁶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、ｐは０または１を示す。）
で表されるジオキセタン化合物（III−１）が、入手の容易性、反応性、低吸湿性、得られる硬化物の力学的特性などの点から好ましく用いられる。

Wherein two R ⁵ are the same or different alkyl groups having 1 to 5 carbon atoms, R ⁶ is a divalent organic group having or not having an aromatic ring, p is 0 or 1 Is shown.)
The dioxetane compound (III-1) represented by the formula is preferably used from the viewpoints of availability, reactivity, low hygroscopicity, and mechanical properties of the resulting cured product.

In the above general formula (III-1), examples of R ⁵ include methyl, ethyl, propyl, butyl, and pentyl. Examples of R ⁶ 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. ), A 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, hydrogenated A bisphenol Z residue, a cyclohexane dimethanol residue, a tricyclodecane dimethanol residue, etc. can be mentioned.

  Specific examples of the dioxetane compound (III-1) represented by the general formula (III-1) include a dioxetane compound represented by the following formula (III-1a) or formula (III-1b). Can do.

（式中、２個のＲ⁵は互いに同じか又は異なる炭素数１〜５のアルキル基、Ｒ⁶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 ^{5 s} are the same or different from each other and have a C 1-5 alkyl group, and R ⁶ represents a divalent organic group having or not having an aromatic ring.)

Specific examples of the dioxetane compound represented by the above formula (III-1a) 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.
Further, specific examples of the dioxetane compound represented by the above formula (III-1b) include, in the above formula (III-1b), two R ^{5 s} are each a methyl, ethyl, propyl, butyl or pentyl group, R ⁶ is an alkylene group such as ethylene group, propylene group, butylene group, neopentylene group, n-pentamethylene group, n-hexamethylene group, formula: —CH ₂ —Ph—CH ₂ — or —CH ₂ —Ph—Ph. Dioxetane which is a divalent group represented by —CH ₂ —, a hydrogenated bisphenol A residue, a hydrogenated bisphenol F residue, a hydrogenated bisphenol Z residue, a cyclohexanedimethanol residue, or a tricyclodecanedimethanol residue A compound can be mentioned.
The resin composition for optical modeling according to the present invention may contain one or more of the dioxetane compounds described above.

Among them, as the polyoxetane compound (OXp), in the above formula (III-1a), bis (3-methyl-3-oxetanylmethyl) ether in which two R ^{5 s} are both methyl groups or ethyl groups and / or Bis (3-ethyl-3-oxetanylmethyl) ether is preferably used from the viewpoints of availability, low hygroscopicity, mechanical properties of the cured product, etc., and in particular, bis (3-ethyl-3-oxetanylmethyl) ether Is more preferably used.

  The resin composition for optical modeling of the present invention is a resin composition for optical modeling from the viewpoint of improvement in toughness of an optical modeling object obtained from the resin composition for optical modeling, mechanical properties, heat resistance, moisture resistance, etc. of the modeling object. Based on the total mass of the cationically polymerizable organic compound (A) in the product, the polyoxetane compound (OXp) is preferably contained in a proportion of 5 to 50% by mass, and contained in a proportion of 5 to 40% by mass. It is more preferable that it is contained at a ratio of 5 to 30% by mass.

The resin composition for optical modeling according to the present invention includes an oxetane group in the molecule together with the alicyclic diglycidyl ether compound (I) and the polyoxetane compound (OXp) as a part of the cationically polymerizable organic compound (A). Containing a monooxetane compound (OXm).
When the resin composition for optical modeling of the present invention contains a polyoxetane compound (OXp) and a monooxetane compound (OXm) as the oxetane compound, the photocuring sensitivity of the resin composition for optical modeling is further increased. In addition, moisture and moisture of the resin composition for optical modeling are further improved in photocuring sensitivity without impairing the absorptivity, and also when the resin composition for optical modeling is stored in a high humidity state for a long period of time. It is possible to suppress the absorption of moisture and to maintain the initial high photocuring sensitivity over a long period of time, and toughness of the resulting three-dimensional structure is further improved.

As the monooxetane compound (OXm), any compound having one oxetane group in one molecule can be used. Among them, a monooxetane compound having one oxetane group and one alcoholic hydroxyl group in one molecule can be used. Oxetane monoalcohol is preferably used in terms of reactivity, viscosity of the composition, and the like.
In particular, among the monooxetane monoalcohol compounds, the monooxetane compound (III-2a) represented by the following general formula (III-2a) and the monooxetane compound represented by the following general formula (III-2b) ( At least one monooxetane compound selected from III-2b) is preferably used from the viewpoints of availability, reactivity, and the like. In particular, when the monooxetane compound (III-2b) represented by the following general formula (III-2b) is used as the monooxetane compound (OXm), the water resistance of the resin composition for optical modeling and the three-dimensional modeled product obtained therefrom The property becomes better.

（式中、Ｒ⁷およびＲ⁸は炭素数１〜５のアルキル基、Ｒ⁹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、ｑは１〜６の整数を示す。）

Wherein R ⁷ and R ⁸ are alkyl groups having 1 to 5 carbon atoms, R ⁹ is an alkylene group having 2 to 10 carbon atoms which may have an ether bond, and q is an integer of 1 to 6. )

In the above general formula (III-2a), examples of R ⁷ include methyl, ethyl, propyl, butyl, and pentyl. In the general formula (III-2a), q may be any one of 1 to 6, but 1 is preferable from the viewpoint of easiness of synthesis.
Specific examples of the monooxetane compound (III-2a) 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 (III-2b), examples of R ⁸ include methyl, ethyl, propyl, butyl, and pentyl.
In the above general formula (III-2b), R ⁹ 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 ( It may be a C2-C10 chain or branched alkylene group having an ether bond (ether oxygen atom) in the middle of the (alkylene chain). Specific examples of R ⁹ include ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, and 3-oxypentylene group. Among these, R ⁹ is preferably a trimethylene group, a tetramethylene group, a pentamethylene group or a heptamethylene group from the viewpoints of ease of synthesis and easy handling of the compound which is liquid at room temperature.

The resin composition for optical modeling of the present invention contains a monooxetane compound (OXm) in a proportion of 2 to 40% by mass based on the total mass of the cationically polymerizable organic compound (A) from the viewpoint of photocurability. It is preferable to contain in the ratio of 2-30 mass%, and it is still more preferable to contain in the ratio of 5-25 mass%.
Further, the content ratio (mass ratio) of the polyoxetane compound (OXp): monooxetane compound (OXm) in the resin composition for optical modeling of the present invention is 5:95 to 95: 5, particularly 10:90 to 80:20. It is preferable that, in addition to the effect of improving the toughness of the optical modeling object, the moisture and moisture absorption rate of the optical modeling resin composition is extremely low, and the optical modeling resin composition is in a high humidity state. When stored for a long period of time, the absorption of moisture and moisture is reduced, and the effect of maintaining the initial high photocuring sensitivity over a long period of time can be achieved.

The resin composition for optical modeling of the present invention suppresses moisture and moisture absorption and maintains a high photocuring sensitivity of the resin composition for optical modeling, so that the moisture resistance of a three-dimensional model obtained by photocuring is further increased. In order to improve the properties, dimensional accuracy, and dimensional stability, it is necessary that the cation polymerizable organic compound having an ester carbonyl group is not substantially contained in the molecule.
As a typical example of the “cationic polymerizable organic compound having an ester carbonyl group in the molecule” that the resin composition for optical modeling of the present invention does not contain, it has an epoxy group and an ecitecarbonyl group in the molecule. A compound etc. can be mentioned. Specific examples of the “cationic polymerizable organic compound having an ester carbonyl group in the molecule” include, but are not limited to, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylcyclohexanecarboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4 -Epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, bis (3 , 4-Epoxycyclohexyl Til) adipate, 3,4-epoxy-6-methylcyclohexylcarboxylate, ethylenebis (3,4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, aliphatic length Polyglycidyl esters of chain polybasic acids, homopolymers synthesized by vinyl polymerization of glycidyl acrylate or glycidyl methacrylate, copolymers synthesized by vinyl polymerization of glycidyl acrylate and / or glycidyl methacrylate and other vinyl monomers, glycidyl esters of higher fatty acids, There are epoxidized soybean oil, epoxy butyl stearate, etc., and the resin composition for optical modeling of the present invention has these cationic polymerizable organic compounds having an ester carbonyl group. Contains no compounds.

  In the resin composition for optical modeling according to the present invention, the total content of the alicyclic diglycidyl ether compound (I), polyoxetane compound (OXp) and monooxetane compound (OXm) having no ester carbonyl group is cationically polymerizable. Based on the total mass of the organic compound (A), it is preferably 40 to 100% by mass, more preferably 60 to 100% by mass, and even more preferably 70 to 100% by mass. By using the above-mentioned content, the curing sensitivity, thick film curability, resolution, ultraviolet transmittance, etc. of the resin composition for optical modeling become better, and the viscosity of the resin composition for optical modeling becomes low and the modeling is smooth. The volumetric shrinkage of the optically shaped object obtained by modeling is further reduced, the toughness of the obtained optically shaped object is increased, and even if stress such as impact and bending is applied, it is difficult to break, In addition, the moisture and moisture absorption rate of the optical modeling resin composition is extremely low, and when the optical modeling resin composition is stored for a long period of time in a high humidity state, the absorption of moisture and moisture is reduced. High photocuring sensitivity can be maintained over a long period of time.

  The resin composition for optical modeling according to the present invention includes, as the cationic polymerizable organic compound (A), a molecule together with the alicyclic diglycidyl ether compound (I), the polyoxetane compound (OXp), and the monooxetane compound (OXm). Other cationically polymerizable organic compounds having no ester carbonyl group can be contained therein as required. As other cationically polymerizable organic compounds that the resin composition for optical modeling of the present invention can contain as necessary, an alicyclic group having no ester carbonyl group other than the alicyclic diglycidyl ether compound (I). Examples thereof include an epoxy compound, an aliphatic epoxy compound having no ester carbonyl group, and an aromatic epoxy compound having no ester carbonyl group. As another epoxy compound, a polyepoxy compound having two or more epoxy groups in one molecule is more preferably used.

  The kind of the other alicyclic epoxy compound which does not have the ester carbonyl group which the resin composition for optical shaping | molding of this invention can contain as needed is not limited, For example, at least 1 alicyclic ring is included. Cyclohexene oxide obtained by epoxidizing a polyglycidyl ether of a polyhydric alcohol having no ester carbonyl group or a compound not having an ester carbonyl group having a cyclohexene or cyclopentene ring with an appropriate oxidizing agent such as hydrogen peroxide or peracid Or a cyclopentene oxide containing compound etc. can be mentioned, Specific examples include 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-metadioxane, dicyclopentadiene diepoxide, Bis (3,4-epoxycyclohexyl ) Methane, 2,2-bis (3,4-epoxycyclohexyl) propane, 1,1-bis (such as 3,4-epoxycyclohexyl) ethane and the like.

  Further, the kind of the aliphatic epoxy compound having no ester carbonyl group in the molecule that the resin composition for optical modeling of the present invention can contain as necessary is not limited, for example, an aliphatic polyhydric alcohol or its Examples include polyglycidyl ethers of alkylene oxide adducts. Specific examples include 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, and trimethylol. Diglycidyl ether of propane, triglycidyl ether of trimethylolpropane, tetraglycidyl ether of sorbitol, hexaglycidyl ether of dipentaerythritol, diglycidyl ether of polyethylene glycol, diglycidyl of polypropylene glycol Polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as propylene, trimethylolpropane and glycerin. And monoglycidyl ether of higher aliphatic alcohol, phenol, cresol, butylphenol, or monoglycidyl ether of polyether alcohol obtained by adding alkylene oxide thereto, epoxidized polybutadiene, and the like.

  In addition, the type of the aromatic epoxy compound having no ester carbonyl group that can be contained as necessary in the resin composition for optical modeling of the present invention is not limited, for example, addition of a polyhydric phenol or an alkylene oxide thereof Specific examples include, for example, bisphenol A, bisphenol F, or glycidyl ethers of compounds obtained by further adding an alkylene oxide such as ethylene oxide or propylene oxide, or glycidyls of novolac resins. An ether etc. can be mentioned.

Examples of the aromatic epoxy compound having no ester carbonyl group include bisphenol A diglycidyl ether (commercially available products such as Epicoat 828 manufactured by Japan Epoxy Resin Co., Ltd., EP-4800 manufactured by Asahi Denka Co., Ltd.), and bisphenol. F diglycidyl ether (Epicoat 807 manufactured by Japan Epoxy Resin Co., Ltd., EP-4900 manufactured by Asahi Denka Co., Ltd.), propylene oxide-modified bisphenol A diglycidyl ether (commercially available product, Rika Resin manufactured by Shin Nippon Chemical Co., Ltd.) BPO-20E, BPO-60E, EP-4000 manufactured by Asahi Denka Co., Ltd.), phenol novolac type epoxy resin (commercially available products are N-730 and N-770 manufactured by Dainippon Ink Chemical Co., Ltd., YDPN638 manufactured by Tohto Kasei Co., Ltd.) Etc.).
Moreover, as a commercial item of the aliphatic epoxy compound which does not have an ester carbonyl group mentioned above, for example, EX-212, EX-313, EX-321, EX-411, EX-521, EX- manufactured by Nagase Gemtech Co., Ltd. 614, EX-711, EX-811, EX-821, EX-851, EX-911, EX-941, EX-920, YH-300, PG-202, PG-207 manufactured by Tohto Kasei Co., Ltd. .

  In the resin composition for optical modeling of the present invention, as part of the cationically polymerizable organic compound (A), an alicyclic diglycidyl ether compound (I) having no ester carbonyl group, a polyoxetane compound (OXp), and a monooxetane When using other cationically polymerizable organic compounds having no ester carbonyl group other than the compound (OXm), the content ratio is 60% by mass based on the total mass of the cationically polymerizable organic compound (A). Is preferably 40% by mass or less, more preferably 30% by mass or less.

  The resin composition for optical modeling according to the present invention includes an active energy ray-sensitive radical polymerization initiator (D) [hereinafter simply referred to as “radical polymerization initiator (D)” or “radical polymerization initiator” as the radical polymerizable organic compound (B). ] In the presence of di- (meth) acrylate compounds (B1) and (meta) having two (meth) acryloyloxy groups that undergo radical polymerization and / or crosslinking when irradiated with ultraviolet rays or other active energy rays. ) Contains a poly (meth) acrylate compound (B2) having 3 or more acryloyloxy groups.

The resin composition for optical modeling according to the present invention includes 20 to 60% by mass of a di (meth) acrylate compound (B1) and a poly (meth) acrylate compound (B2) based on the total mass of the radical polymerizable organic compound (B). ) Is preferably contained in a proportion of 30 to 70% by mass, the di (meth) acrylate compound (B1) in a proportion of 25 to 50% by mass and the poly (meth) acrylate compound (B2) in a proportion of 40 to 60% by mass. It is more preferable to contain.
In addition, the content ratio (mass ratio) of the di (meth) acrylate compound (B1): poly (meth) acrylate compound (B2) in the resin composition for optical modeling is preferably 20:80 to 70:30, It is more preferable that it is 30: 70-60: 40.
By containing the di (meth) acrylate compound (B1) and the poly (meth) acrylate compound (B2) in the above-described ratio, the resin composition for optical modeling is excellent in photocurability, and the resulting three-dimensional modeled product is obtained. Shows excellent mechanical strength.
When the radically polymerizable organic compound (B) contains the di (meth) acrylate compound (B1) but does not contain the poly (meth) acrylate compound (B2), the mechanical properties become inferior. When the (meth) acrylate compound (B2) is contained but the di (meth) acrylate compound (B1) is not contained, the toughness of the photocured product becomes inferior, and the object of the present invention cannot be achieved.

  As the di (meth) acrylate compound (B1), any di (meth) acrylate compound having two (meth) acryloyloxy groups in the molecule can be used, and an epoxy compound and (meth) acrylic acid can be used. Examples include di (meth) acrylates obtained by reaction, di (meth) acrylic acid esters of dihydric alcohols, polyester di (meth) acrylates, di (meth) acrylates of polyether diols, and the like.

  As di (meth) acrylate obtained by reaction of the above-mentioned epoxy compound and (meth) acrylic acid, aromatic epoxy compound, alicyclic epoxy compound and / or aliphatic epoxy compound, and (meth) acrylic acid Mention may be made of di (meth) acrylate-based reaction products obtained by the reaction. Among the di (meth) acrylate reaction products described above, di (meth) acrylate reaction products obtained by reaction of an aromatic epoxy compound and (meth) acrylic acid are preferably used. As specific examples, An epoxy (meth) acrylate obtained by reacting diglycidyl ether such as bisphenol A or bisphenol S with (meth) acrylic acid can be used.

The di (meth) acrylic acid esters of dihydric alcohols described above include aromatic alcohols, aliphatic alcohols, alicyclic alcohols and / or their alkylene oxide adducts having two hydroxyl groups in the molecule. , Di (meth) acrylate obtained by reaction with (meth) acrylic acid. Specific examples include 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 ( And (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, and di (meth) acrylate of an alkylene oxide adduct of the diol described above.
Of the di (meth) acrylate compounds described above, diacrylate compounds are preferably used from the viewpoint of polymerization rate rather than dimethacrylate compounds.

  Furthermore, examples of the di (meth) acrylate of the above-described polyester diol 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.

  Among them, in the present invention, as the di (meth) acrylate compound (B1), one or two of di (meth) acrylate of ethylene oxide-modified bisphenol A and di (meth) acrylate of bis (hydroxymethyltricyclodecane) are used. Is preferably used.

  In addition, as the poly (meth) acrylate compound (B2), a reaction product having three or more (meth) acryloyloxy groups obtained by reacting an epoxy compound with (meth) acrylic acid, a trivalent or higher polyvalent Poly (meth) acrylic acid ester of an alcohol or its alkylene oxide adduct, polyethylene poly having three or more (meth) acryloyloxy groups obtained by reacting a polyester having three or more hydroxyl groups and (meth) acrylate A (meth) acrylate etc. can be mentioned.

As a specific example of the reaction product having three or more (meth) acryloyloxy groups obtained by reacting the epoxy compound with (meth) acrylic acid, an epoxy novolac resin and (meth) acrylic acid are reacted. An epoxy (meth) acrylate reaction product having three or more (meth) acryloyloxy groups obtained can be exemplified.
Examples of the poly (meth) acrylate obtained by reacting a trihydric or higher polyhydric alcohol or an alkylene oxide adduct thereof with (meth) acrylic acid include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, Examples include dipentaerythritol hexa (meth) acrylate and (meth) acrylates of alkylene oxide adducts of polyhydric alcohols such as triol, tetraol, and hexaol described above.
Among them, in the present invention, as the poly (meth) acrylate compound (B2), dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, or a modified alkylene oxide thereof is preferably used.

  The resin composition for optical modeling according to the present invention includes, as the radical polymerizable organic compound (B), other diradicals as necessary together with the di (meth) acrylate compound (B1) and the poly (meth) acrylate compound (B2). A polymerizable organic compound can be contained. In the case of containing another radical polymerizable organic compound, the content ratio is preferably 30% by mass or less, and 20% by mass or less based on the total mass of the radical polymerizable organic compound (B). Is more preferable.

The kind of the other radical polymerizable organic compound that the resin composition for optical modeling of the present invention can contain as necessary is not particularly limited. For example, mono (meth) having one (meth) acryloyloxy group. An acrylate compound, an unsaturated polyester compound, a polythiol compound, etc. can be mentioned, These other radically polymerizable organic compounds may be used individually, or may use 2 or more types together.
Specific examples of the mono (meth) acrylate compound described above include 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth). Examples include acrylate, isooctyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, and benzyl (meth) acrylate. Besides these, imide acrylate compounds can also be used, and specific examples include N- (2-acryloyloxyethyl) tetrahydrophthalimide, N- (2-acryloyloxyethyl) hexahydrophthalimide and the like. it can.

  The resin composition for optical modeling according to the present invention has the following general formula (II) as a cationic polymerization initiator (C) for polymerizing and / or crosslinking the cationic polymerizable organic compound (A);

で表されるアンチモンの芳香族スルホニウム化合物（II）［以下「アンチモン芳香族スルホニウム化合物（II）」という］を含有する。
アンチモン芳香族スルホニウム化合物（II）は、式：［Ｓ⁺（Ｒ²）_a（Ｒ³）_b（Ｒ⁴）_c］で表されるカチオンと、式：［Ｓｂ^-Ｆ₆］で表されるアニオンが、イオン結合した塩である。
アンチモン芳香族スルホニウム化合物（II）において、Ｒ²およびＲ³は、それぞれ独立して下記の式（ｉ）で表されるフェニル基、式（ii）で表される塩化フェニル基またはフルオロフェニル基、式（iii）で表される４−フェニルチオフェニル基或いは式（iv）で表される基である［式（ii）および（iv）において、Ｘは塩素原子またはフッ素原子を示す］。

And an antimony aromatic sulfonium compound (II) represented by the formula (hereinafter referred to as “antimony aromatic sulfonium compound (II)”).
The antimony aromatic sulfonium compound (II) is represented by a cation represented by the formula: [S ⁺ (R ² ) _a (R ³ ) _b (R ⁴ ) _c ] and a formula: [Sb ⁻ F ₆ ]. An anion is a salt that is ion-bonded.
In the antimony aromatic sulfonium compound (II), R ² and R ³ are each independently a phenyl group represented by the following formula (i), a phenyl chloride group or a fluorophenyl group represented by the formula (ii), A 4-phenylthiophenyl group represented by the formula (iii) or a group represented by the formula (iv) [in the formulas (ii) and (iv), X represents a chlorine atom or a fluorine atom].

アンチモン芳香族スルホニウム化合物（II）では、Ｒ²とＲ³は同じであっても、または異なっていてもよい。
また、アンチモン芳香族スルホニウム化合物（II）において、Ｒ⁴は、下記の式（ｖ）で表される４’−ジフェニルスルホニオ−４−フェニルチオフェニル基である。

In the antimony aromatic sulfonium compound (II), R ² and R ³ may be the same or different.
In the antimony aromatic sulfonium compound (II), R ⁴ is a 4′-diphenylsulfonio-4-phenylthiophenyl group represented by the following formula (v).

  In the antimony aromatic sulfonium compound (II), a and b are both integers of 0 to 3, c is 0 or 1, and the sum of a, b and c is 3. Therefore, in the aromatic sulfonium compound (II), the sum of a and b is 3 or 2, and c is 0 or 1.

In general formula (II), m is the same number as 1 + c.
In the general formula (II), when c is 0 and the cation of the antimony aromatic sulfonium compound (II) does not have R ⁴ [group represented by the above formula (v)], m is 1. is there.
Further, when c is 1 and the cation of the antimony aromatic sulfonium compound (II) has one R ⁴ [group represented by the above formula (v)] in the general formula (II), the formula: [ The cation represented by S ⁺ (R ² ) _a (R ³ ) _b (R ⁴ ) _c ] is a divalent cation, and two anions: [Sb ⁻ F ₆ ] are included in the divalent cation. Ion-bonded (m = 2).

Specific examples of the cation represented by the formula: [S ⁺ (R ² ) _a (R ³ ) _b (R ⁴ ) _c ] in the antimony aromatic sulfonium compound (II) include, but are not limited to, And cations (IIa ₁ ) to (IIa ₅ ).

  Specific examples of the antimony aromatic sulfonium compound (II) preferably used in the present invention include compounds represented by the following formulas (II-1) to (II-3), or a mixture thereof. Can do.

Specific examples of the antimony aromatic sulfonium compound (II) include triphenylsulfonium hexafluoroantimonate, diphenyl- [4- (phenylthio) phenyl] sulfonium hexafluoroantimonate, 4,4′-bis (diphenylsulfonio). Phenyl sulfide-bis-hexafluoroantimonate, 4,4′-bis [di (β-hydroxyethoxy) phenylsulfonio] phenyl sulfide-bis-hexafluoroantimonate, 4- [4 ′-(benzoyl) phenylthio] Tria such as phenyl-di- (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4-benzoylphenylthio) phenyl-di- (4-fluorophenyl) sulfonium hexafluoroantimonate Examples thereof include a reel sulfonium salt and a mixture thereof. Commercially available products include “UVI-6974” manufactured by Dow, “CPI-101A” manufactured by Sun Apro, “SP-172” manufactured by ADEKA, and the like.
In the present invention, one or more of the above-described antimony aromatic sulfonium compounds can be used.

In the resin composition for optical modeling according to the present invention, an active energy ray-sensitive radical polymerization initiator (D) for polymerizing and / or crosslinking the radical polymerizable organic compound (B) [hereinafter referred to as “radical polymerization initiator (D)”]. As the “radical polymerization initiator”, any polymerization initiator capable of initiating radical polymerization of a radical polymerizable organic compound when irradiated with active energy rays can be used. For example, benzyl or a dialkyl acetal compound thereof Benzoyl compounds, acetophenone compounds, benzoin or alkyl ether compounds thereof, benzophenone compounds, thioxanthone compounds, and the like.
Specifically, examples of benzyl or a dialkyl acetal compound thereof include benzyl dimethyl ketal and benzyl-β-methoxyethyl acetal. Examples of the benzoyl compound include 1-hydroxycyclohexyl phenyl ketone.
Examples of the acetophenone compound include diethoxyacetophenone, 2-hydroxymethyl-1-phenylpropan-1-one, 4′-isopropyl-2-hydroxy-2-methyl-propiophenone, and 2-hydroxy-2. -Methyl-propiophenone, p-dimethylaminoacetophenone, p-tert-butyldichloroacetophenone, p-tert-butyltrichloroacetophenone, p-azidobenzalacetophenone and the like.

Examples of 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.

  In the resin composition for optical modeling of the present invention, the content ratio of cationic polymerizable organic compound (A): radical polymerizable organic compound (B) is 30:70 to 90:10 from the viewpoint of modeling speed, curing accuracy, and the like. (Mass ratio) is preferable, and 40:60 to 85:15 (mass ratio) is more preferable. Moreover, the resin composition for optical shaping | molding of this invention is 0.1-10 mass of antimony aromatic sulfonium compound (II) [cationic polymerization initiator (C)] based on the mass of a cationically polymerizable organic compound (A). %, Particularly 1 to 5% by mass, and the radical polymerization initiator (D) is 0.1 to 20% by mass, particularly 1 to 10% by mass, based on the mass of the radical polymerizable organic compound (B). It is preferable to contain by a ratio.

  The resin composition for optical modeling according to the present invention may further contain a photosensitizer, for example, dialkoxyanthracene such as dibutoxyanthracene, thioxanthone, or the like, if necessary, for the purpose of improving the reaction rate.

In addition, the resin composition for optical modeling of the present invention can optionally contain a polyalkylene ether compound, and if it contains a polyalkylene ether compound, the impact resistance of the resulting three-dimensional modeled object, etc. Physical properties are further improved.
As the polyalkylene ether compound, in particular, the following general formula (IV):

A—O— (R ¹⁰ —O—) _r — (R ¹¹ —O—) _s —A ′ (IV)

[Wherein, R ¹⁰ and R ¹¹ are linear or branched alkylene groups having 2 to 5 carbon atoms different from each other, A and A ′ each independently represent a hydrogen atom, an alkyl group, or a phenyl group; Each s independently represents 0 or an integer of 1 or more (provided that both r and s are not 0 at the same time). ]
A polyalkylene ether compound represented by the formula is preferably used.

In the polyalkylene ether compound represented by the above general formula (IV) [hereinafter sometimes referred to as “polyalkylene ether compound (IV)”], both r and s are integers of 1 or more, and r and s Are 3 or more, oxyalkylene units (alkylene ether units): —R ¹⁰ —O— and oxyalkyne units (alkylene ether units): —R ¹¹ —O— are bonded in a random manner. Alternatively, they may be combined in a block shape, or random bonds and block bonds may be mixed.

In the polyalkylene ether compound (IV), specific examples of R ¹⁰ and R ¹¹ include ethylene group, n-propylene group, isopropylene group, n-butylene group (tetramethylene group), isobutylene group, tert- Butylene group, linear or branched pentylene group [for example, —CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ —, —CH ₂ CH ₂ CH (CH ₃ ) CH ₂ — etc.], etc.] . Among them, R ¹⁰ and R ¹¹ are ethylene group, n-propylene group, isopropylene group, n-butylene group (tetramethylene group), n-pentylene group, formula: —CH ₂ CH ₂ CH (CH ₃ ) CH It is preferably any one of branched pentylene groups represented by _2- .

  In the polyalkylene ether compound (IV), specific examples of A and A ′ include a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a phenyl group, an acetyl group, and a benzoyl group. Among them, it is preferable that at least one of A and A ′, in particular, both are hydrogen atoms. When at least one of A and A ′ is a hydrogen atom, both ends of the polyalkylene ether compound are obtained when the resin composition for optical modeling containing the polyalkylene ether compound is cured by irradiation with active energy rays. These hydroxyl groups react with an epoxy compound, a radical polymerization initiator, and the like, and the polyalkylene ether compound is bonded in the cured resin, and properties such as impact resistance are further improved.

  In the above polyalkylene ether compound (IV), r and s indicating the number of repeating oxyalkylene units are within the range of the number average molecular weight of the polyalkylene ether compound of 500 to 10,000, particularly 500 to 5,000. The number is preferably such that

Suitable examples of the polyalkylene ether compound (IV) include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyethylene oxide-polypropylene oxide block copolymer, random copolymer of ethylene oxide and propylene oxide, formula An oxytetramethylene unit (alkyl-substituted) having an alkyl substituent represented by: —CH ₂ CH ₂ CH (R ¹² ) CH ₂ O— (wherein R ¹² is a lower alkyl group, preferably a methyl or ethyl group). A polyether having a tetramethylene ether group having a group), the oxytetramethylene unit and the formula: —CH ₂ CH ₂ CH (R ¹² ) CH ₂ O— (wherein R ¹² is a lower alkyl group). Oxytetramethylene with an alkyl substituent There may be mentioned polyether bonded randomly. Among them, a polytetramethylene glycol and / or tetramethylene ether unit having a number average molecular weight in the range of 500 to 10,000 described above and a formula: —CH ₂ CH ₂ CH (R ¹² ) CH ₂ O— (wherein R ¹² is a polyether in which tetramethylene ether units having an alkyl substituent represented by a lower alkyl group are randomly bonded. In that case, the hygroscopic property is low, and the dimensional stability and physical property stability are reduced. An excellent stereolithography can be obtained.

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

Moreover, the resin composition for optical shaping | molding of this invention is the following general formula (V);

HO—R ¹³ —OH (V)

(In the formula, R ¹³ represents a linear or branched alkylene group having 5 to 8 carbon atoms.)
May contain at least one selected from the group consisting of bifunctional hydroxy compounds (V).
When the bifunctional hydroxy compound (V) is contained in the resin composition for optical modeling according to the present invention, the moisture content is extremely lowered even if it is stored for a long time in a low humidity state such as when it is dried in winter. In addition, moisture necessary for photocuring (generally 0.3 to 1% by mass, preferably 0.4 to 0.8% by mass) is stably retained in the composition. However, in order to improve the curing sensitivity of the resin composition for optical modeling, a high curing sensitivity can be maintained without adding moisture from the outside.
When the bifunctional hydroxy compound (V) is contained, the content thereof is 1 to 10% by mass based on the mass of the resin composition for optical modeling, further 1 to 7% by mass, particularly 1 to 5% by mass. Preferably there is.

Specific examples of the bifunctional hydroxy compound (V) include bifunctional hydroxy compounds in which R ¹³ is an alkylene group having 5 carbon atoms [for example, HO—CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ —OH, HO—CH. _{(CH 3) CH 2 CH 2} CH 2 -OH, HO-CH 2 CH (CH 3) CH 2 CH 2 -OH, HO-CH (CH 3) CH (CH 3) CH 2 -OH, HO-C ( CH ₃ ) ₂ CH ₂ CH ₂ —OH, HO—CH ₂ C (CH ₃ ) ₂ CH ₂ —OH]; a bifunctional hydroxy compound in which R ² is a C 6 alkylene group [eg, HO—CH ₂ CH _{2 CH 2 CH 2 CH 2 CH} 2 -OH, HO-CH (CH 3) CH 2 CH 2 CH 2 CH 2 -OH, HO-CH 2 CH (CH 3) CH 2 CH 2 CH 2 -OH, HO- _{CH 2 CH 2 CH (CH 3} ) CH 2 CH 2 -OH, HO-CH (CH _{3) CH (CH 3) CH} 2 CH 2 -OH, HO-CH 2 CH (CH 3) CH (CH 3) CH 2 -OH, HO-CH (CH 3) CH 2 CH (CH 3) 2 CH 2 _{-OH, HO-CH (CH 3} ) CH 2 CH 2 CH (CH 3) -OH, HO-CH (CH 3) CH (CH 3) CH (CH 3) -OH, HO-C (CH 3) 2 _{CH (CH 3) CH 2 -OH} , HO-C (CH 3) 2 CH 2 CH (CH 3) -OH, HO-CH 2 CH (CH 3) 2 CH (CH 3) -OH, HO-CH 2 CH ₂ CH (C ₂ H ₅ ) CH ₂ —OH and the like]; a bifunctional hydroxy compound in which R ¹³ is an alkylene group having 7 carbon atoms [for example, HO—CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH _{2 -OH, HO-CH (CH 3} ) CH 2 CH 2 CH 2 CH 2 CH 2 -OH, HO-CH 2 CH (CH 3) C _{2 CH 2 CH 2 CH 2 -OH} , HO-CH 2 CH 2 CH (CH 3) CH 2 CH 2 CH 2 -OH, HO-CH (CH 3) CH (CH 3) CH 2 CH 2 CH 2 -OH _{, HO-CH 2 CH (CH} 3) CH (CH 3) CH 2 CH 2 -OH, HO-CH (CH 3) CH 2 CH (CH 3) 2 CH 2 CH 2 -OH, HO-CH (CH 3 _{) CH 2 CH 2 CH 2 CH} (CH 3) -OH, HO-CH (CH 3) CH (CH 3) CH (CH 3) CH 2 -OH, HO-C (CH 3) 2 CH (CH 3) _{CH 2 CH 2 -OH, HO-} C (CH 3) 2 CH 2 CH (CH 3) CH 2 -OH, HO-CH 2 CH (CH 3) 2 CH (CH 3) CH 2 -OH, HO-CH ₂ CH ₂ CH (C ₂ H ₅ ) CH ₂ CH ₂ —OH, etc.]; R ¹³ bifunctional hydroxy compound which is an alkylene group having a prime number of 8 Object [for example _{HO-CH 2 CH 2 CH 2} CH 2 CH 2 CH 2 CH 2 CH 2 -OH, HO-CH (CH 3) CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 -OH, HO-CH 2 _{CH (CH 3) CH 2 CH} 2 CH 2 CH 2 CH 2 -OH, HO-CH 2 CH 2 CH (CH 3) CH 2 CH 2 CH 2 CH 2 -OH, HO-CH (CH 3) CH (CH _{3) CH 2 CH 2 CH 2} CH 2 -OH, HO-CH 2 CH (CH 3) CH (CH 3) CH 2 CH 2 CH 2 -OH, HO-CH (CH 3) CH 2 CH (CH 3) _{2 CH 2 CH 2 CH 2 -OH} , HO-CH (CH 3) CH 2 CH 2 CH (CH 3) CH 2 CH 2 -OH, HO-C (CH 3) 2 CH (CH 3) CH 2 CH 2 _{CH 2 -OH, HO-C (} CH 3) 2 CH 2 CH (CH 3) CH 2 CH 2 -OH, HO-CH 2 CH ₂ CH (C ₂ H ₅ ) CH ₂ CH ₂ CH ₂ —OH, etc.], CH ₃ (CH ₂ ) ₅ CH (OH) CH ₂ OH, etc., and one or more of these may be used. be able to.
Among these, as the bifunctional hydroxy compound (V), neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, and 1,8-octanediol are available. In terms of hygroscopicity, moisture retention, and reactivity, neopentyl glycol and 1,6-hexanediol are particularly preferably used.

  The resin composition for optical modeling of the present invention is a colorant such as a pigment or a dye, an antifoaming agent, a leveling agent, a thickener, a flame retardant, or an antioxidant, as necessary, unless the effects of the present invention are impaired. Further, it may contain an appropriate amount of one kind or two or more kinds of fillers (crosslinked polymer particles, silica, glass powder, ceramic powder, metal powder, etc.) and a modifying resin.

For optically three-dimensional modeling using the resin composition for optical modeling of the present invention, any conventionally known optical three-dimensional modeling method and apparatus can be used. As a representative example of the optical three-dimensional modeling method that can be preferably adopted, the active energy ray is selectively irradiated so that a cured layer having a desired pattern is obtained in the liquid resin composition for optical modeling of the present invention. Then, a cured layer is formed, and then an uncured liquid optical modeling resin composition is supplied to the cured layer, and similarly, a cured layer continuous with the cured layer is formed by irradiating active energy rays. The method of finally obtaining the target three-dimensional molded item can be mentioned by repeating lamination | stacking operation.
Examples of 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.

  In forming each cured resin layer having a predetermined shape pattern by irradiating active energy rays onto a modeling surface made of a resin composition for optical modeling, active energy rays narrowed to a point like a laser beam are used. It may be used to form a cured resin layer by dot or line drawing, or through a planar drawing mask formed by arranging multiple micro light shutters such as liquid crystal shutters or digital micromirror shutters (DMD). You may employ | adopt the modeling system which irradiates a surface with an active energy ray planarly and forms a cured resin layer.

  The resin composition for optical modeling of the present invention can be widely used in the field of optical three-dimensional modeling and is not limited at all, but as a typical application field, in order to verify the appearance design in the middle of the design Shape verification models, functional test models for checking the functionality of parts, master models for producing molds, master models for producing molds, direct molds for prototype molds, and the like. In particular, the resin composition for optical modeling according to the present invention is very effective for producing a shape confirmation model or a function test model of a precise part. 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.
Moreover, in the following examples, it was obtained by measuring the viscosity, moisture absorption rate, curing depth (Dp), critical curing energy (Ec) and work curing energy (E ₁₀ ) of the resin composition for optical modeling, and optical modeling. Mechanical properties [Tensile properties (tensile strength, tensile elongation at break, tensile modulus), bending properties (flexural strength, flexural modulus)], shrinkage rate, hardness, thermal deformation temperature and humidity 80% The measurement or calculation of the elongation at was performed as follows.

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

(2) Moisture absorption rate of resin composition for stereolithography:
100 g of the resin composition for optical modeling produced in the following examples or comparative examples was placed in a beaker (capacity: 100 ml) and contained in a desiccator (capacity: 5000 ml) adjusted to a humidity of 80%, and allowed to stand at a temperature of 25 ° C. for 14 days. After placement, the moisture (water content) (mass%) contained in the resin composition for stereolithography is taken out from the desiccator, and the volumetric titration moisture measuring device (“Model KF-06” manufactured by Mitsubishi Chemical Corporation) Was measured using.

(3) Depth of curing (Dp), critical curing energy (Ec) and work curing energy (E ₁₀ ) of the resin composition for stereolithography:
Measurement was performed according to the theory described in Non-Patent Document 1. Specifically, a laser beam (ultraviolet light with a wavelength of 355 nm, a liquid surface laser intensity of 100 mW) of a semiconductor-excited solid laser is applied to a modeling surface (liquid surface) made of a resin composition for optical modeling, and the irradiation speed is changed in six steps ( The photocured film was formed by irradiating with the irradiation energy amount changed by 6 levels. The produced photocured film was taken out from the resin composition liquid for photofabrication, the uncured resin was removed, and the thickness of the cured film corresponding to six levels of energy was measured with a vernier caliper. Plotting the photocured film thickness as the Y-axis and the irradiation energy amount as the X-axis (logarithmic axis), obtaining the cure depth [Dp (mm)] from the slope of the straight line obtained by plotting, and intercepting the X-axis Was the critical curing energy [Ec (mJ / cm ² )], and the exposure energy required to cure to a thickness of 0.25 mm was the work curing energy [(E ₁₀ / (mJ / cm ² )].

(4) Tensile properties of the optically shaped object (tensile strength, tensile elongation at break, tensile modulus):
In accordance with JIS K-7113, the tensile strength, tensile rupture elongation, and tensile strength of the test piece were used in accordance with JIS K-7113, using the optically shaped article (dumbbell-shaped test piece conforming to JIS K-7113) prepared in the following examples or comparative examples The elastic modulus was measured.

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

(6) Shrinkage rate:
From the specific gravity (d ₀ ) of the resin composition for optical modeling (liquid) before photo-curing and the specific gravity (d ₁ ) of the photo-cured product obtained by photo-curing, the shrinkage rate was determined by the following formula.

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

(7) Hardness of stereolithography (Shore D hardness):
Using the "ASKER D-type hardness meter" manufactured by Kobunshi Keiki Co., Ltd., using the stereolithography (dumbbell-shaped test piece conforming to JIS K-7113) produced in the following examples and comparative examples, Based on K-6253, the hardness (Shore D hardness) of the test piece was measured by the durometer method.

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

(9) Elongation rate of stereolithography under 80% humidity:
The rectangular string-shaped stereolithography product (length × width × thickness = 200 mm × 10 mm × 1 mm) produced in the following examples or comparative examples was put in a desiccator adjusted to a humidity of 80% at a temperature of 25 ° C. After leaving as it is for 14 days, it was taken out from the desiccator, the length was measured, and the elongation (%) with respect to the length (200 mm) before being put in the desiccator was obtained.

Example 1
(1) 54 parts of hydrogenated bisphenol A diglycidyl ether (“HBE-100” manufactured by Shin Nippon Chemical Co., Ltd.), 10 parts of bis (3-ethyl-3-oxetanylmethyl) ether, 3-hydroxymethyl-3-ethyloxetane 5 parts, 15 parts of tricyclodecane dimethanol diacrylate (“A-DCP” manufactured by Shin-Nakamura Chemical Co., Ltd.), 9 parts of dipentaerythritol hexaacrylate (“NK ester A-9530” manufactured by Shin-Nakamura Chemical Co., Ltd.) Antimony aromatic sulfonium compound (II-1) represented by the above formula (II-1) (diphenyl [4- (phenylthio) phenyl] sulfonium hexafluoroantimonate) (“CPI-101A” manufactured by San Apro) 3 .5 parts, 1-hydroxy-cyclohexyl phenyl ketone (Ciba Specialty) 2 parts "Irgacure-184", radical polymerization initiator) and 0.03 part of Tinuvin 384-2 (UV absorber; manufactured by Ciba Specialty Chemicals) were mixed well at room temperature (25 ° C). Thus, a resin composition for stereolithography was prepared. It was 470 mPa * s (25 degreeC) when the viscosity of this resin composition for optical shaping | molding was measured by the above-mentioned method.
(2) When the curing depth (Dp), critical curing energy (Ec), and work curing energy (E ₁₀ ) of the resin composition for optical modeling obtained in (1) above were measured by the methods described above, the following table was obtained. 1 as shown.
(3) A semiconductor laser (rated output: 1000 mW; wavelength: 355 nm) using an ultrahigh-speed stereolithography system (“SOLIFORM500B” manufactured by Nabtesco Corporation) using the resin composition for stereolithography obtained in (1) above; Spectra Physics "semiconductor-excited solid laser BL6 type", with a liquid level of 500 mW and a liquid level irradiation energy of 80 mJ / cm ² , a slice pitch (lamination thickness) of 0.10 mm and an average modeling time of 2 minutes per layer The optical three-dimensional modeling is performed to produce a dumbbell-shaped test piece according to JIS K-7113 for measuring physical properties, a bar-shaped test piece according to JIS K-7171, and a rectangular string-shaped shaped article. The physical properties were measured by the method described above, and the results are shown in Table 1 below.

<< Comparative Example 1 >>
(1) As in (1) of Example 1, except that 15 parts of 3-hydroxymethyl-3-ethyloxetane was used as the oxetane compound without using bis (3-ethyl-3-oxetanylmethyl) ether. Then, a resin composition for optical modeling was prepared, and the physical properties of this resin composition for optical modeling were measured in the same manner as in (2) of Example 1, and as shown in Table 1 below.
(2) Using the resin composition for optical modeling obtained in (1) above, optical three-dimensional modeling is performed in the same manner as (3) of Example 1, and the three-dimensional modeled object (test piece) obtained. When the physical properties of were measured, they were as shown in Table 1 below.

<< Comparative Example 2 >>
(1) As in (1) of Example 1, except that 15 parts of bis (3-ethyl-3-oxetanylmethyl) ether was used as the oxetane compound without using 3-hydroxymethyl-3-ethyloxetane. Then, a resin composition for optical modeling was prepared, and the physical properties of this resin composition for optical modeling were measured in the same manner as in (2) of Example 1, and as shown in Table 1 below.
(2) Using the resin composition for optical modeling obtained in (1) above, optical three-dimensional modeling is performed in the same manner as (3) of Example 1, and the three-dimensional modeled object (test piece) obtained. When the physical properties of were measured, they were as shown in Table 1 below.

<< Comparative Example 3 >>
(1) In place of 54 parts of hydrogenated bisphenol A diglycidyl ether, 50 parts of hydrogenated bisphenol A diglycidyl ether and 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate (manufactured by DOW Chemical, USA) Except for using 4 parts of “UVR-6105”), a resin composition for optical modeling was prepared in the same manner as in (1) of Example 1, and the physical properties of this resin composition for optical modeling were When measured in the same manner as 2), it was as shown in Table 1 below.
(2) Using the resin composition for optical modeling obtained in (1) above, optical three-dimensional modeling is performed in the same manner as (3) of Example 1, and the three-dimensional modeled object (test piece) obtained. When the physical properties of were measured, they were as shown in Table 1 below.

<< Comparative Example 4 >>
(1) In place of 54 parts of hydrogenated bisphenol A diglycidyl ether, 50 parts of hydrogenated bisphenol A diglycidyl ether and 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate (manufactured by DOW Chemical, USA) "UVR-6105")) was used except that 4 parts were used, and 15 parts of bis (3-ethyl-3-oxetanylmethyl) ether was used as the oxetane compound without using 3-hydroxymethyl-3-ethyloxetane. A resin composition for optical modeling was prepared in the same manner as (1) in Example 1, and the physical properties of this resin composition for optical modeling were measured in the same manner as (2) in Example 1. It was as shown.
(2) Using the resin composition for optical modeling obtained in (1) above, optical three-dimensional modeling is performed in the same manner as (3) of Example 1, and the three-dimensional modeled object (test piece) obtained. When the physical properties of were measured, they were as shown in Table 1 below.

<< Comparative Example 5 >>
(1) In place of 54 parts of hydrogenated bisphenol A diglycidyl ether, 50 parts of hydrogenated bisphenol A diglycidyl ether and 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate (manufactured by DOW Chemical, USA) "UVR-6105") was used except that 4 parts were used, and 15 parts of 3-hydroxymethyl-3-ethyloxetane was used as the oxetane compound without using bis (3-ethyl-3-oxetanylmethyl) ether. A resin composition for optical modeling was prepared in the same manner as (1) in Example 1, and the physical properties of this resin composition for optical modeling were measured in the same manner as (2) in Example 1. It was as shown.
(2) Using the resin composition for optical modeling obtained in (1) above, optical three-dimensional modeling is performed in the same manner as (3) of Example 1, and the three-dimensional modeled object (test piece) obtained. When the physical properties of were measured, they were as shown in Table 1 below.

<< Comparative Example 6 >>
(1) Resin for photofabrication in the same manner as (1) of Example 1 except that, as a radical polymerizable organic compound, dipentaerythritol hexaacrylate 24 portion was used without using tricyclodecane dimethanol diacrylate. A composition was prepared, and the physical properties of the resin composition for optical modeling were measured in the same manner as in Example 1 (2). The results were as shown in Table 1 below.
(2) Using the resin composition for optical modeling obtained in (1) above, optical three-dimensional modeling is performed in the same manner as (3) of Example 1, and the three-dimensional modeled object (test piece) obtained. When the physical properties of were measured, they were as shown in Table 1 below. In addition, in the three-dimensional molded item obtained in this Comparative Example 6, warpage occurred and the dimensional accuracy was inferior.

As can be seen from the results in Table 1 above, the resin composition for photofabrication of Example 1 containing an antimony aromatic sulfonium compound (II) as a cationic polymerization initiator is an ester in the molecule as a cationic polymerizable organic compound. Without containing a cation-polymerizable organic compound having a carbonyl group, the alicyclic diglycidyl ether compound (I) (hydrogenated bisphenol A diglycidyl ether), polyoxetane compound (OXp) [bis (3-ethyl-3- Oxetanylmethyl) ether] and monooxetane compound (OXm) (3-hydroxymethyl-3-ethyloxetane), and di (meth) acrylate compound (B1) (tricyclodecane dimethanol dimethyl) as a radical polymerizable organic compound. Acrylate) and poly (meth) acrylate compound (B2) ( By containing both (pentaerythritol hexaacrylate), it is possible to produce a three-dimensional modeled product with high photocuring sensitivity and high productivity, low moisture absorption (moisture absorption 0.6 mass%), and storage. It is excellent in stability and handleability, and the three-dimensional structure obtained by photocuring the resin composition for optical modeling of Example 1 has an elongation rate of 0.3% under a high humidity of 80%. Small, less moisture and moisture absorption, excellent dimensional stability and dimensional accuracy of three-dimensional objects, and mechanical properties such as tensile strength, tensile elongation at break, tensile elastic modulus, bending strength, bending elastic modulus It has excellent characteristics, is hard to break, has excellent durability, and has excellent heat resistance.
Yes.

  On the other hand, the resin composition for optical modeling of Comparative Example 1 containing an antimony aromatic sulfonium compound (II) as a cationic polymerization initiator does not contain a cationically polymerizable organic compound having an ester carbonyl group, It contains di (meth) acrylate compound (B1) and poly (meth) acrylate compound (B2) together with cyclic diglycidyl ether compound (I), but it contains only monooxetane compound (OXm) as oxetane compound. , Since it does not contain a polyoxetane compound (OXp), compared with the resin composition for optical modeling of Example 1, the moisture absorption rate in the resin composition for optical modeling before curing is significantly higher and storage stability, The three-dimensional structure obtained in Example 1 is obtained by using the resin composition for optical modeling according to Comparative Example 1 which is inferior in handleability. Base, the tensile strength, tensile elongation at break, tensile elastic modulus, is inferior in all of flexural strength.

  Moreover, the resin composition for optical modeling of Comparative Example 2 containing an antimony aromatic sulfonium compound (II) as a cationic polymerization initiator does not contain a cationically polymerizable organic compound having an ester carbonyl group and is alicyclic. Although it contains di (meth) acrylate compound (B1) and poly (meth) acrylate compound (B2) together with diglycidyl ether compound (I), it contains only polyoxetane compound (OXp) as an oxetane compound, Since it does not contain an oxetane compound (OXm), the curing reaction rate is slow, and the three-dimensional structure obtained by photocuring the resin composition for optical modeling of Comparative Example 2 is the resin composition for optical modeling of Example 1. Compared to a three-dimensional structure obtained from an object, the tensile elongation at break and bending strength are significantly lower, and the mechanical properties are inferior.

  Moreover, the resin composition for optical modeling of Comparative Example 3 contains an alicyclic diglycidyl ether compound (I), a polyoxetane compound (OXp), and a monooxetane compound (OXm), and is a dipolymer as a radical polymerizable organic compound. Although it contains both the (meth) acrylate compound (B1) and the poly (meth) acrylate compound (B2), it also contains a cationically polymerizable organic compound having an ester carbonyl group. The composition and the three-dimensional structure obtained therefrom have high hygroscopicity, and the storage stability of the resin composition for optical modeling, the dimensional stability and the dimensional accuracy of the three-dimensional structure are inferior. Moreover, the three-dimensional structure obtained from the resin composition for optical modeling according to Comparative Example 3 is higher in tensile elongation at break and tensile modulus than the three-dimensional object obtained from the resin composition for optical modeling according to Example 1. The bending strength and flexural modulus are significantly small, the mechanical properties are inferior, the toughness is inferior, the material is brittle, and the heat distortion temperature is low and the heat resistance is also inferior.

  The resin composition for optical modeling of Comparative Example 4 includes an alicyclic diglycidyl ether compound (I), a polyoxetane compound (OXp), a di (meth) acrylate compound (B1), and a poly (meth) acrylate compound (B2). It contains, but does not contain a monooxetane compound (OXm), while it contains a cationically polymerizable organic compound having an ester carbonyl group. The three-dimensional structure has a high hygroscopic property, and the storage stability of the resin composition for optical modeling, the dimensional stability and the dimensional accuracy of the three-dimensional structure are inferior. Moreover, the three-dimensional model obtained from the resin composition for optical modeling of Comparative Example 4 is higher in tensile strength, tensile elongation at break than the three-dimensional model obtained from the resin composition for optical modeling of Example 1. Bending strength and flexural modulus are small, mechanical properties are inferior, toughness is inferior, brittle, thermal deformation temperature is low, and heat resistance is inferior.

  The resin composition for optical modeling according to Comparative Example 5 includes an alicyclic diglycidyl ether compound (I), a monooxetane compound (OXm), a di (meth) acrylate compound (B1), and a poly (meth) acrylate compound (B2). Although it does not contain a polyoxetane compound (OXp), on the other hand, it contains a cationically polymerizable organic compound having an ester carbonyl group, the resin composition for stereolithography and the solid obtained therefrom The model has a high hygroscopic property, and the storage stability of the resin composition for optical modeling, the dimensional stability and the dimensional accuracy of the three-dimensional model are poor. In addition, the three-dimensional object obtained from the resin composition for optical modeling of Comparative Example 5 is higher in tensile strength, tensile elongation at break than the three-dimensional object obtained from the resin composition for optical modeling of Example 1. Tensile modulus, flexural strength and flexural modulus are significantly small, inferior in mechanical properties, inferior in toughness, brittle, in addition, have low heat deformation temperature and inferior heat resistance.

  The resin composition for optical modeling of Comparative Example 6 contains an alicyclic diglycidyl ether compound (I), a polyoxetane compound (OXp), and a monooxetane compound (OXm), and a cationically polymerizable organic compound having an ester carbonyl group However, it contains only the poly (meth) acrylate compound (B2) as the radical polymerizable organic compound, and does not contain the di (meth) acrylate compound (B1). The three-dimensional structure obtained from the product has significantly lower tensile strength, tensile elongation at break, and bending strength than the three-dimensional structure obtained from the resin composition for optical modeling of Example 1, and has mechanical properties. It was inferior to toughness, inferior toughness, brittle, warped and inferior in dimensional accuracy.

Example 2
(1) Example 1 except that 54 parts of 1,4-cyclohexanedimethanol diglycidyl ether (“DME-100”, manufactured by Shin Nippon Chemical Co., Ltd.) was used instead of 54 parts of hydrogenated bisphenol A diglycidyl ether. The resin composition for optical modeling was prepared in the same manner as in (1), and the physical properties of this resin composition for optical modeling were measured in the same manner as in (2) of Example 1, as shown in Table 2 below. Met.
(2) Using the resin composition for optical modeling obtained in (1) above, optical three-dimensional modeling is performed in the same manner as (3) of Example 1, and the three-dimensional modeled object (test piece) obtained. When the physical properties of were measured, they were as shown in Table 2 below.

Example 3
(1) Instead of 10 parts of bis (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis (3-ethyl-3-oxetanylmethoxymethyl) benzene (“OXT-121” manufactured by Toagosei Co., Ltd.) Except for using 10 parts, a resin composition for optical modeling was prepared in the same manner as (1) of Example 2, and the physical properties of this resin composition for optical modeling were the same as (2) of Example 1. When measured, it was as shown in Table 2 below.
(2) Using the resin composition for optical modeling obtained in (1) above, optical three-dimensional modeling is performed in the same manner as (3) of Example 1, and the three-dimensional modeled object (test piece) obtained. When the physical properties of were measured, they were as shown in Table 2 below.

Example 4
(1) Instead of 3.5 parts of the antimony aromatic sulfonium compound (II-1) (diphenyl [4- (phenylthio) phenyl] sulfonium hexafluoroantimonate) (cationic polymerization initiator) used in Example 2, (4-Fluorophenyl)-[(4-benzoyl-2-chlorophenyl) thiophenyl] sulfonium hexafluoroantimonate [antimony aromatic sulfonium compound represented by the above formula (II-2), “SP-172” manufactured by ADEKA ]] A resin composition for optical modeling was prepared in the same manner as (1) of Example 2 except that 3.5 parts were used, and the physical properties of this resin composition for optical modeling were changed to (2) of Example 1. Was measured in the same manner as shown in Table 2 below.
(2) Using the resin composition for optical modeling obtained in (1) above, optical three-dimensional modeling is performed in the same manner as (3) of Example 1, and the three-dimensional modeled object (test piece) obtained. When the physical properties of were measured, they were as shown in Table 2 below.

The resin composition for photofabrication of the present invention containing an antimony aromatic sulfonium compound (II) as a photocationic polymerization initiator is photocured even though it does not contain a cationically polymerizable organic compound having an ester carbonyl group. Highly sensitive and capable of producing the desired three-dimensional model with a short modeling time with high productivity and absorption of moisture and moisture by not containing a cationically polymerizable organic compound having an ester carbonyl group The three-dimensional structure obtained by using the resin composition for optical modeling of the present invention is excellent in dimensional stability due to its low moisture absorption, and further has toughness and durability, and other mechanics. Excellent in mechanical properties, water resistance, moisture resistance, heat resistance, etc.
Therefore, using the resin composition for stereolithography of the present invention, models for precision parts, electrical / electronic parts, furniture, building structures, automobile parts, various containers, castings, molds, mother molds, etc. High modeling speed and dimensions for machining models, parts for designing complex heat transfer circuits, parts for analysis planning of heat transfer behavior of complex structures, and other three-dimensional objects with complicated shapes and structures Accurate and safe to manufacture.

Claims (9)

(I) An optical steric composition containing a cationically polymerizable organic compound (A), a radically polymerizable organic compound (B), an active energy ray sensitive cationic polymerization initiator (C) and an active energy ray sensitive radical polymerization initiator (D). A resin composition for modeling;
(Ii) As the cationically polymerizable organic compound (A),
The following general formula (I):

(In the formula, R ¹ represents a hydrogenated bisphenol A residue, a hydrogenated bisphenol F residue, a hydrogenated bisphenol Z residue, a cyclohexanedimethanol residue or a tricyclodecanedimethanol residue.)
An alicyclic diglycidyl ether compound (I) represented by:
A polyoxetane compound (OXp) having two or more oxetane groups; and
A monooxetane compound having one oxetane group (OXm);
Containing;
(Iii) As radically polymerizable organic compound (B),
A di (meth) acrylate compound (B1) having two (meth) acryloyloxy groups; and
A poly (meth) acrylate compound (B2) having 3 or more (meth) acryloyloxy groups;
Containing;
(Iv) The active energy ray-sensitive cationic polymerization initiator (C) is represented by the following general formula (II):

[In the above formula (II), R ² and R ³ are each independently the following formulas (i) to (iv);

{In Formula (ii) and Formula (iv), X represents a chlorine atom or a fluorine atom}
In which R ⁴ is represented by the following formula (v):

A is an integer of 0 to 3, b is an integer of 0 to 3, and c is 0 or 1, and the sum of a, b and c is 3, and m is the same as 1 + c. Is a number. ]
An aromatic sulfonium compound (II) of antimony represented by:
(V) substantially free of a cationically polymerizable organic compound having an ester carbonyl group in the molecule;
A resin composition for optical three-dimensional modeling characterized by the above.   The content ratio of the cationic polymerizable organic compound (A): radical polymerizable organic compound (B) is 30:70 to 90:10, and the antimony aromatic sulfonium compound (II) is converted to a cationic polymerizable organic compound ( It contains in the ratio of 0.1-10 mass% based on the mass of A), and an active energy ray sensitive radical polymerization initiator (D) is 0.1-20 based on the mass of a radically polymerizable organic compound (B). The resin composition for optical three-dimensional model | molding of Claim 1 contained in the ratio of the mass%.   3. The optical three-dimensional modeling according to claim 1, comprising the alicyclic diglycidyl ether compound (I) at a ratio of 20 to 95% by mass based on the total mass of the cationically polymerizable organic compound (A). Resin composition.   The polyoxetane compound (OXp) is contained in an amount of 5 to 50% by mass and the monooxetane compound (OXm) in a proportion of 2 to 40% by mass based on the total mass of the cationically polymerizable organic compound (A). The resin composition for optical three-dimensional modeling of any one of these.   The total content of the alicyclic diglycidyl ether compound (I), the polyoxetane compound (OXp) and the monooxetane compound (OXm) based on the total mass of the cationically polymerizable organic compound (A) is 40 to 100% by mass. Item 5. The resin composition for optical three-dimensional modeling according to any one of Items 1 to 4.   Based on the total mass of the radical polymerizable organic compound (B), the di (meth) acrylate compound (B1) is contained in a proportion of 20 to 60% by mass and the poly (meth) acrylate compound (B2) in a proportion of 30 to 70% by mass. The resin composition for optical three-dimensional modeling according to any one of claims 1 to 5. The polyoxetane compound (OXp) is represented by the following general formula (III-1);

Wherein two R ⁵ are the same or different alkyl groups having 1 to 5 carbon atoms, R ⁶ is a divalent organic group having or not having an aromatic ring, p is 0 or 1 Is shown.)
The resin composition for optical three-dimensional model | molding of any one of Claims 1-6 which is a dioxetane compound represented by these. The monooxetane compound (OXm) is a monooxetane compound (III-2a) represented by the following general formula (III-2a) and a monooxetane compound (III-2b) represented by the following general formula (III-2b) The resin composition for optical three-dimensional model | molding of any one of Claims 1-7 which is the at least 1 sort (s) of monooxetane compound chosen from these.

Wherein R ⁷ and R ⁸ are alkyl groups having 1 to 5 carbon atoms, R ⁹ is an alkylene group having 2 to 10 carbon atoms which may have an ether bond, and q is an integer of 1 to 6. )   The method to manufacture an optical three-dimensional molded item using the resin composition for optical three-dimensional modeling of any one of Claims 1-8.