JPWO2013172406A1 - Optical three-dimensional resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition for optical three-dimensional modeling that does not contain a toxic antimony cationic polymerization initiator, is excellent in safety and handleability, is not yellowed, is colorless and transparent, and has excellent color tone and appearance. Offer. SOLUTION: A cationically polymerizable organic compound, a radically polymerizable organic compound, a cationic polymerization initiator and a radical polymerization initiator are contained. As the cationic polymerization initiator, an aromatic sulfonium compound of the following general formula (C-1) and the following A resin composition for optical three-dimensional modeling containing an aromatic sulfonium compound of the general formula (C-2). [In the above general formulas (C-1) and (C-2), R1, R2, R3, R4, R5 and R6 are monovalent organic groups, Rf is a fluoroalkyl group, and m is the above general formula. In (C-1), “the same number as the cation number of the cation [S + (R1) (R2) (R3)], n is an integer of 1 to 5 and p is the number in the above general formula (C-2)” It is the same number as the cation number of the cation [S + (R4) (R5) (R6)].] [Selection] None

Description

  The present invention relates to a resin composition for optical three-dimensional modeling and a method for producing an optical three-dimensional model using the composition. More specifically, the present invention relates to an optical three-dimensional modeling composition containing a non-antimony cationic polymerization initiator that is excellent in safety and free of environmental pollution, and the optical three-dimensional modeling resin of the present invention. By using the composition, with high curing sensitivity, while preventing pollution of the global environment, it has a low yellowness and a high total light transmittance and is colorless or transparent or close to it, and toughness, other An optical three-dimensional structure excellent in mechanical properties, water resistance, and the like can be produced safely and with high productivity at high modeling speed.

  Resin composition for optical three-dimensional modeling containing a cationic polymerizable organic compound and a cationic polymerization initiator, a resin composition for optical three-dimensional modeling containing a radical polymerizable organic compound and a radical polymerization initiator, a cationic polymerizable organic compound, Various types of resin compositions for optical three-dimensional modeling such as a resin composition for optical three-dimensional modeling containing a radical polymerizable organic compound, a cationic polymerization initiator, and a radical polymerization initiator have been conventionally proposed.

Among them, in a resin composition for optical three-dimensional modeling containing a cationically polymerizable organic compound such as an epoxy compound, a cationic polymerization initiator existing in the system generates a cationic species (H ⁺ ) by light irradiation, which is chained. In particular, the cation polymerizable organic compound is ring-opened due to the cation polymerizable organic compound such as an epoxy compound, 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. The shrinkage rate of the photocured product is small, and a shaped product with good dimensional accuracy can be obtained.

  Cationic polymerization initiators for photopolymerizing cationically polymerizable organic compounds include aromatic sulfonium salts of Group VIIa elements (see Patent Document 1) and aromatic onium salts of Group VIa elements (see Patent Document 2). In addition, a cationic photopolymerization initiator made of an aromatic onium salt of a Group Va element (see Patent Document 3) is known. Among them, a sulfonium salt containing antimony has been widely used as a photocationic polymerization initiator in a photocurable resin composition containing a cationically polymerizable organic compound.

However, since antimony compounds are generally toxic and exhibit toxic effects similar to arsenic and mercury, it is necessary to pay close attention to handling, and there are concerns about contamination of the work environment and the global environment.
From this point, a resin composition for optical three-dimensional modeling using a cationic polymerization initiator composed of a sulfonium salt containing phosphorus instead of the conventionally used antimony cationic polymerization initiator has been proposed (Patent Literature). 4, 5, 6).
However, cationic polymerization initiators composed of phosphorus-containing sulfonium salts are less cationic when exposed to light because the acidity (cationic species) generated by light irradiation is lower than that of antimony cationic polymerization initiators. The catalyst activity as an initiator is low, and it is often impossible to obtain a three-dimensional structure with satisfactory physical properties.

Under such circumstances, among the cationic polymerization initiators composed of a sulfonium salt containing phosphorus, the phosphoric cationic polymerization initiator composed of a phosphate having an anion moiety having a fluoroalkyl group is a conventional antimony-based cationic polymerization initiator. It is known to have the same photopolymerization initiating ability as that of an agent, but a resin composition for optical three-dimensional modeling is prepared using a phosphorous cationic polymerization initiator composed of a phosphate having an anion moiety having a fluoroalkyl group. And when optical modeling is performed using the said resin composition for optical three-dimensional modeling, the color tone of the three-dimensional molded item obtained becomes light yellow, and the three-dimensional molded item which has a colorless and transparent or close color tone is not obtained. In particular, the anion moiety is a cation of a phosphorus-based sulfonium salt, which is a trifluorotris (fluoroalkyl) phosphate ion represented by the formula: [PF ₃ (Rf) ₃ ⁻ ] (wherein Rf is a fluoroalkyl group). When used as a polymerization initiator, there is a problem that the yellowness of the resulting three-dimensional model increases, and the color gradually becomes darker when placed at room temperature.
The three-dimensional object obtained by optical modeling using the optical three-dimensional resin composition is a model for verifying the appearance design of various industrial products during the design, a model for checking the functionality of the parts, It is widely used as a resin mold for manufacturing molds, a base model for manufacturing molds, etc., and in recent years there is a model with high transparency and no yellowing like lenses of automobiles and motorcycles. Phosphorus-based cations that are highly safe because they are used in the field of arts and crafts such as restoration of artworks, imitation and contemporary art, and design presentation models for glass-walled buildings. Optical three-dimensional modeling that gives a three-dimensional modeled article that has high transparency and is not colored yellow even for a resin composition for optical three-dimensional modeling containing a polymerization initiator The resin composition has been required.

  In addition, for a three-dimensional model obtained by optical modeling of a resin composition for optical three-dimensional modeling, it is required to be excellent in toughness, strong and not easily damaged. It has been proposed to contain a polyalkylene ether compound in the resin composition for use. However, with the expansion of the use of the resin composition for optical three-dimensional modeling and the three-dimensional model obtained by optical modeling using the same, the three-dimensional model having further improved toughness can be manufactured. There is a need for resin compositions.

Japanese Examined Patent Publication No. 52-14277 Japanese Patent Publication No.52-14278 Japanese Patent Publication No.52-14279 JP 2007-262401 A JP 2007-238828 A JP 2011-89088 A

It is an object of the present invention to contain no toxic antimony cationic polymerization initiator as a cationic polymerization initiator, thereby being excellent in safety and handling, and not being yellowish, colorless and transparent, or close to it, in color and appearance. It is providing the resin composition for optical three-dimensional model | molding which can manufacture the three-dimensional model | molding thing which is excellent in A.
Furthermore, the object of the present invention is to produce a three-dimensional molded article that is excellent in toughness, strong and not easily damaged, in addition to the above-described characteristics of safety and colorless transparency, and has high photocuring sensitivity, For optical 3D modeling, 3D objects can be produced with high productivity in a shortened optical modeling time, and 3D objects with excellent dimensional accuracy, other mechanical properties, and heat resistance can be formed. It is to provide a resin composition.

  The present inventors have made various studies in order to achieve the above object. As a result, in the resin composition for optical three-dimensional modeling containing a cationic polymerizable organic compound, a radical polymerizable organic compound, a cationic polymerization initiator, and a radical polymerization initiator, a specific phosphorus-based aromatic as a cationic polymerization initiator When combined with a sulfonium salt, a three-dimensional structure with a low yellowness, colorless transparency, or a color tone and appearance close to it, while exhibiting high catalytic activity equivalent to that obtained when an antimony cationic polymerization initiator is used. I found.

Furthermore, when the present inventors further include at least one kind of dye selected from a purple dye and a blue dye in the resin composition for optical three-dimensional modeling, the yellowness is further reduced and colorless and transparent It has been found that a three-dimensionally shaped article with improved properties can be obtained.
In addition, in the above-described resin composition for optical three-dimensional modeling, the inventors of the present invention performed stereolithography when diglycidyl ether of a specific alicyclic diol is contained at a predetermined ratio as the cationic polymerizable organic compound. It discovered that the transparency of the three-dimensional molded article obtained improved further.
Furthermore, when the present inventors include a specific polyalkylene ether compound and polyalkylene ether di (meth) acrylate in the resin composition for optical three-dimensional modeling, a three-dimensional molded product with further improved toughness can be obtained. The present invention was completed based on these findings.

That is, the present invention
(1) A resin composition for optical three-dimensional modeling comprising a cationically polymerizable organic compound (A), a radically polymerizable organic compound (B), a cationic polymerization initiator (C) and a radical polymerization initiator (D). The cationic polymerization initiator (C) is represented by the following general formula (C-2) and at least one aromatic sulfonium compound (C-1) represented by the following general formula (C-1). The resin composition for optical three-dimensional model | molding characterized by including at least 1 sort (s) of an aromatic sulfonium compound.

［上記の一般式（Ｃ−１）および一般式（Ｃ−２）中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵およびＲ⁶は１価の有機基、Ｒｆはフルオロアルキル基、ｍは上記の一般式（Ｃ−１）における「カチオン［Ｓ⁺（Ｒ¹）（Ｒ²）（Ｒ³）］が有する陽イオン価と同じ数、ｎは１〜５の整数およびｐは上記の一般式（Ｃ−２）における「カチオン［Ｓ⁺（Ｒ⁴）（Ｒ⁵）（Ｒ⁶）］が有する陽イオン価と同じ数である。］

[In the above general formulas (C-1) and (C-2), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are monovalent organic groups, Rf is a fluoroalkyl group, m is the same number as the cation number of “cation [S ⁺ (R ¹ ) (R ² ) (R ³ )]” in the above general formula (C-1), n is an integer of 1 to 5, and p is the above In general formula (C-2), “the same number as the cation number of the cation [S ⁺ (R ⁴ ) (R ⁵ ) (R ⁶ )].”

And this invention,
(2) Resin for optical three-dimensional model | molding of said (1) whose content rate of aromatic sulfonium compound (C-1): aromatic sulfonium compound (C-2) is mass ratio of 90: 10-60: 40. A composition; and
(3) The optical ratio of (1) or (2), wherein the content ratio of the aromatic sulfonium compound (C-1): aromatic sulfonium compound (C-2) is a mass ratio of 85:15 to 70:30. Three-dimensional modeling resin composition;
It is.

Furthermore, the present invention provides
(4) R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ in the general formula (C-1) and the general formula (C-2) are each independently bonded to an aromatic ring. A monovalent aromatic group which may have a substituent, having one or more bonds represented by the formulas: —S—, —SO—, —O— and —CO—. And a resin composition for optical three-dimensional modeling according to any one of (1) to (3), which is a monovalent aromatic group that does or does not have; and
(5) R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ in the above general formula (C-1) and general formula (C-2) are each independently represented by the following general formula << The resin composition for optical three-dimensional modeling according to any one of (1) to (4), which is any group represented by 1 >> to << 11 >>;
It is.

［式中、Ｒ⁷、Ｒ⁸、Ｒ⁹、Ｒ¹⁰、Ｒ¹¹、Ｒ¹²、Ｒ¹³、Ｒ¹⁴、Ｒ¹⁵、Ｒ¹⁶、Ｒ¹⁷およびＲ¹⁸は、それぞれ独立して、置換基を有していてもよいアルキル基またはアリール基であり、Ｘ¹、Ｘ²、Ｘ³、Ｘ⁴、Ｘ⁵、Ｘ⁶、Ｘ⁷、Ｘ⁸、Ｘ⁹、Ｘ¹⁰、Ｘ¹¹、Ｘ¹²、Ｘ¹³、Ｘ¹⁴、Ｘ¹⁵、Ｘ¹⁶、Ｘ¹⁷、Ｘ¹⁸、Ｘ¹⁹、Ｘ²⁰、Ｘ²¹およびＸ²²は、それぞれ独立して、アルキル基、アリール基、アルコキシ基、アリールオキシ基、ヒドロキシ（ポリ）アルキレンオキシ基、水酸基、シアノ基、ニトロ基およびハロゲン原子から選ばれる基であり、Ｚ¹、Ｚ²、Ｚ³およびＺ⁴は、それぞれ独立して、式：−Ｓ−、−ＳＯ−および−Ｏ−から選ばれる２価の基であり、それぞれ独立してｄ¹は０〜５の整数、ｄ²、ｄ³およびｄ⁴は０〜４の整数、ｄ⁵は０〜５の整数、ｄ⁶、ｄ⁷、ｄ⁸、ｄ⁹、ｄ¹⁰、ｄ¹¹、ｄ¹²、ｄ¹³、ｄ¹⁴、ｄ¹⁵およびｄ¹⁶は０〜４の整数、ｄ¹⁷は０〜５の整数、ｄ¹⁸は０〜４の整数、ｄ¹⁹は０〜５の整数、ｄ²⁰、ｄ²¹およびｄ²²は０〜５の整数である。］

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

The present invention also provides:
(6) As the cationically polymerizable organic compound (A), the following general formula (A-1);

（式中、Ｒ¹⁹は、水素添加ビスフェノールＡ残基、水素添加ビスフェノールＥ残基、水素添加ビスフェノールＦ残基、水素添加ビスフェノールＡＤ残基、水素添加ビスフェノールＺ残基、シクロヘキサンジメタノール残基またはトリシクロデカンジメタノール残基を示す。）
で表される脂環式ジグリシジルエーテル化合物（Ａ−１）を、カチオン重合性有機化合物（Ａ）の全質量に基づいて５０〜１００質量％の割合で含有する前記（１）〜（５）のいずれかの光学的立体造形用樹脂組成物である。

Wherein R ¹⁹ is hydrogenated bisphenol A residue, hydrogenated bisphenol E residue, hydrogenated bisphenol F residue, hydrogenated bisphenol AD residue, hydrogenated bisphenol Z residue, cyclohexanedimethanol residue or trimethyl Cyclodecanedimethanol residue is shown.)
Said (1)-(5) which contains the alicyclic diglycidyl ether compound (A-1) represented by these in the ratio of 50-100 mass% based on the total mass of a cationically polymerizable organic compound (A). Any one of the resin compositions for optical three-dimensional modeling.

And this invention,
(7) Optical in any one of said (1)-(6) which contains an oxetane compound (A-2) in the ratio of 1-35 mass% based on the mass of a cationically polymerizable organic compound (A). Three-dimensional modeling resin composition;
(8) The optical system according to any one of (1) to (7), wherein the polyalkylene glycol di (meth) acrylate is contained at a ratio of 1 to 20% by mass based on the mass of the radical polymerizable organic compound (B). Three-dimensional modeling resin composition; and
(9) The content ratio of the cationic polymerizable organic compound (A): radical polymerizable organic compound (B) is 30:70 to 90:10 (mass ratio), and the cationic polymerization initiator (C) is replaced with the cationic polymerizable organic compound. It is contained at a ratio of 0.1 to 10% by mass based on the mass of the compound (A), and the radical polymerization initiator (D) is 0.1 to 10% by mass based on the mass of the radical polymerizable organic compound (B). The resin composition for optical three-dimensional modeling according to any one of (1) to (8), which is contained at a ratio of
It is.

Furthermore, the present invention provides
(10) The following general formula (E);
^{Q-O- (R 20 -O-)} q- (R 21 -O-) r-Q '(E)
[Wherein, R ²⁰ and R ²¹ are linear or branched alkylene groups having 2 to 5 carbon atoms, and Q and Q ′ are each independently a hydrogen atom, an alkyl group, a phenyl group, an acetyl group, or benzoyl. And q and r each independently represent 0 or an integer of 1 or more (provided that both q and r cannot be 0 at the same time). ]
(1) to (9) further containing a polyalkylene ether compound (E) represented by the formula (1) to (9) in a proportion of 0.5 to 30% by mass based on the total mass of the resin composition for optical three-dimensional modeling. Any one of the resin compositions for optical three-dimensional modeling.

The present invention also provides:
(11) The above (1) further containing at least one dye (F) selected from a purple dye and a blue dye in an amount of 0.01 to 10 ppm, based on the total mass of the resin composition for optical three-dimensional modeling. ) To (10), the resin composition for optical three-dimensional modeling.
Furthermore, the present invention provides
(12) A method for producing a three-dimensional model by performing optical three-dimensional modeling using the resin composition for optical three-dimensional modeling according to any one of (1) to (11).

The resin composition for optical three-dimensional modeling of the present invention does not contain a toxic antimony-based cationic polymerization initiator, and an aromatic sulfonium compound that is a phosphorus-based aromatic sulfonium salt (C) as a cationic polymerization initiator (C) Since C-1) and the aromatic sulfonium compound (C-2) are contained, it is excellent in safety and handleability.
In the resin composition for optical three-dimensional modeling of the present invention, since the aromatic sulfonium compound (C-1) and the aromatic sulfonium compound (C-2) are used in combination as the cationic polymerization initiator (C), phosphorus Resin composition for optical three-dimensional modeling containing an aromatic sulfonium compound (C-1) alone as a cationic polymerization initiator (C) in spite of using an aromatic sulfonium salt as a cationic polymerization initiator In comparison, the three-dimensional modeled object obtained by optical modeling has a low yellowness and a high light transmittance and is colorless and transparent or has a good color tone and appearance.
The resin composition for optical three-dimensional model | molding of this invention containing at least 1 sort (s) of dye (F) chosen from a purple dye and a blue dye with an aromatic sulfonium compound (C-1) and an aromatic sulfonium compound (C-2) By using an object, it is possible to produce a three-dimensional structure that has a lower yellowness and is more excellent in colorless transparency.

For the optical three-dimensional modeling of the present invention containing, as the cationic polymerization initiator (C), a combination of an aromatic sulfonium compound (C-1) and an aromatic sulfonium compound (C-2) which are phosphorus aromatic sulfonium salts The resin composition has good curing sensitivity to light and sufficient photocuring compared to the resin composition for optical three-dimensional modeling containing the aromatic sulfonium compound (C-1) alone as a cationic polymerization initiator. Therefore, it is possible to manufacture a three-dimensional structure that is excellent in mechanical properties such as strength, elastic properties, and impact resistance.
The resin composition for optical three-dimensional model | molding of this invention contains the alicyclic diglycidyl ether compound (A-1) represented by said general formula (A-1) as a cationically polymerizable organic compound (A). By using the resin composition for optical three-dimensional modeling, a three-dimensional molded product that is further excellent in transparency can be manufactured.
In the resin composition for optical three-dimensional modeling of the present invention, toughness is obtained by using the resin composition for optical three-dimensional modeling containing polyalkylene ether glycol di (meth) acrylate and / or polyalkylene ether, particularly both of them. It is possible to produce a three-dimensional model that is excellent in strength and is hard to break.

  By optical modeling using the resin composition for optical three-dimensional modeling of the present invention, it has a low yellowness and a high light transmittance and is colorless and transparent or has a good color tone and appearance close to it, and has strength and elastic properties. Since the three-dimensional molded article having excellent mechanical properties such as impact resistance and toughness can be produced, the resin composition for optical three-dimensional modeling of the present invention has high transparency and appearance and color tone without yellow coloring. Models and parts for verifying the appearance design of various industrial products in the middle of the design, in which three-dimensional objects that are excellent in mechanical properties such as strength, elasticity, impact resistance, and toughness are required Model for checking functionality, resin mold for making molds, base model for making molds, automobile and motorcycle lenses, restoration of works of art, imitation and modern art, glazed Effectively used in various applications such as arts and crafts fields such as building design presentation models, precision parts, electrical / electronic parts, furniture, building structures, automotive parts, various containers, castings, etc. be able to.

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

In the resin composition for optical three-dimensional model | molding of this invention, the cationic polymerization start which consists of an above-described aromatic sulfonium compound (C-1) and aromatic sulfonium compound (C-2) as a cationically polymerizable organic compound (A). Any compound can be used as long as it is an organic compound that causes a cationic polymerization reaction and / or a cationic crosslinking reaction when irradiated with active energy rays in the presence of the agent (C).
Representative examples of the cationically polymerizable organic compound (A) that can be used in the present invention include epoxy compounds, oxetane compounds and other cyclic ether compounds, cyclic acetal compounds, cyclic lactone compounds, spiro orthoester compounds, vinyl ether compounds, and the like. These cationically polymerizable organic compounds may be used alone or in combination of two or more.
Among these, in the present invention, an epoxy compound and an oxetane compound are preferably used as the cationically polymerizable organic compound (A).

  Examples of the epoxy compound that can be used as the cationically polymerizable organic compound (A) in the present invention include epoxy compounds such as alicyclic epoxy compounds, aliphatic epoxy compounds, and aromatic epoxy compounds.

Examples of the alicyclic epoxy compounds include polyglycidyl ethers of polyhydric alcohols having at least one alicyclic ring, cyclohexene ring-containing compounds, or cyclopentene ring-containing compounds such as hydrogen peroxide and peracid. Examples thereof include a cyclohexene oxide structure-containing compound or a cyclopentene oxide structure-containing compound obtained by epoxidation with an agent. More specifically, as an alicyclic epoxy compound, for example,
The following general formula (A-1);

（式中、Ｒ¹⁹は、水素添加ビスフェノールＡ残基、水素添加ビスフェノールＥ残基、水素添加ビスフェノールＦ残基、水素添加ビスフェノールＡＤ残基、水素添加ビスフェノールＺ残基、シクロヘキサンジメタノール残基またはトリシクロデカンジメタノール残基を示す。）
で表される脂環式ジグリシジルエーテル化合物（Ａ−１）（具体的には、水素添加ビスフェノールＡジグリシジルエーテル、水素添加ビスフェノールＥジグリシジルエーテル、水素添加ビスフェノールＦジグリシジルエーテル、水素添加ビスフェノールＡＤジグリシジルエーテル、水素添加ビスフェノールＺジグリシジルエーテル、シクロヘキサンジメタノールジグリシジルエーテル、トリシクロデカンジメタノールジグリシジルエーテル）を挙げることができる。

Wherein R ¹⁹ is hydrogenated bisphenol A residue, hydrogenated bisphenol E residue, hydrogenated bisphenol F residue, hydrogenated bisphenol AD residue, hydrogenated bisphenol Z residue, cyclohexanedimethanol residue or trimethyl Cyclodecanedimethanol residue is shown.)
(Specifically hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol E diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol AD) Diglycidyl ether, hydrogenated bisphenol Z diglycidyl ether, cyclohexane dimethanol diglycidyl ether, tricyclodecane dimethanol diglycidyl ether).

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

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

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

In the present invention, one or more of the above-described epoxy compounds can be used as the cationic polymerizable organic compound (A), and in one molecule based on the total mass of the cationic polymerizable organic compound (A). It is preferable to contain a polyepoxy compound having two or more epoxy groups in a proportion of 30% by mass or more.
Among them, the resin composition for optical three-dimensional modeling of the present invention is obtained by replacing the alicyclic diglycidyl ether compound (A-1) represented by the general formula (A-1) with a resin composition for optical three-dimensional modeling. Based on the total mass of the cationically polymerizable organic compound (A) contained in, it is particularly preferred to contain 10 to 100% by mass, more preferably 30 to 90% by mass, and particularly preferably 50 to 80% by mass. By containing the alicyclic diglycidyl ether compound (A-1) in an amount within the above range, the transparency of the three-dimensional object obtained by optical modeling is further improved, and the time-dependent dimension of the three-dimensional object is obtained. Stability, water resistance, moisture resistance, and heat resistance are excellent.

Further, as the oxetane compound (A-2), one or more of a monooxetane compound having one oxetane group in one molecule and a polyoxetane compound having two or more oxentane groups in one molecule are used. Can be used.
In particular, the oxetane compound (A-2) is used as a part of the cationically polymerizable organic compound (A), and at that time, the oxetane compound (A-2) is a monooxetane compound having one oxetane group in one molecule ( A-2a) and a polyoxetane compound (A-2b) having two or more oxentane groups in one molecule are converted into a monooxetane compound (A-2a): polyoxetane compound (A-2b) = 95: 5 to 5: When used at a mass ratio of 95, further 10:90 to 90:10, particularly 20:80 to 20:80, the moisture and moisture of the resin composition for optical three-dimensional modeling in a high humidity state The initial high curing sensitivity can be maintained over a long period of time, and the toughness of the three-dimensional structure obtained by optical modeling is improved.

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

（式中、Ｒ²²およびＲ²³は炭素数１〜５のアルキル基、Ｒ²⁴はエーテル結合を有していてもよい炭素数２〜１０のアルキレン基を示す。）

(In the formula, R ²² and R ²³ represent an alkyl group having 1 to 5 carbon atoms, and R ²⁴ represents an alkylene group having 2 to 10 carbon atoms which may have an ether bond.)

In the above general formula (A-2a ₁ ), examples of R ²² include methyl, ethyl, propyl, butyl, and pentyl.
Specific examples of monooxetane alcohol (A-2a ₁ ) include 3-hydroxymethyl-3-methyloxetane, 3-hydroxymethyl-3-ethyloxetane, 3-hydroxymethyl-3-propyloxetane, and 3-hydroxymethyl- 3-normal butyl oxetane, 3-hydroxymethyl-3-propyl oxetane, etc. can be mentioned, These 1 type (s) or 2 or more types can be used. Among these, 3-hydroxymethyl-3-methyloxetane and 3-hydroxymethyl-3-ethyloxetane are more preferably used from the viewpoints of easy availability and reactivity.

In the above general formula (A-2a ₂ ), examples of R ²³ include methyl, ethyl, propyl, butyl, and pentyl.
In the above general formula (A-2a ₂ ), R ²⁴ may be either a chain alkylene group or a branched alkylene group as long as it is an alkylene group having 2 to 10 carbon atoms, or an alkylene group. A C2-C10 chain or branched alkylene group having an ether bond (ether oxygen atom) in the middle of the (alkylene chain) may be used. Specific examples of R ²⁴ include ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, and 3-oxypentylene group. Among them, R ²⁴ is preferably a trimethylene group, a tetramethylene group, a pentamethylene group or a heptamethylene group from the viewpoints of easiness of synthesis and easy handling since the compound is liquid at normal temperature.

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

（式中、２個のＲ²⁵は互いに同じかまたは異なる炭素数１〜５のアルキル基、Ｒ²⁶は芳香環を有しているかまたは有していない２価の有機基、ｓは０または１を示す。）
で表されるジオキセタン化合物（Ａ−２ｂ₀）が、入手性、反応性、低吸湿性、硬化物の力学的特性などの点から好ましく用いられる。
上記の一般式（Ａ−２ｂ₀）において、Ｒ²⁵の例としては、メチル、エチル、プロピル、ブチル、ペンチルを挙げることができる。また、Ｒ²⁶の例としては、炭素数１〜１２の直鎖状または分岐状のアルキレン基（例えばエチレン基、プロピレン基、ブチレン基、ネオペンチレン基、ｎ−ペンタメチレン基、ｎ−ヘキサメチレン基など）、式：−ＣＨ₂−Ｐｈ−ＣＨ₂−または−ＣＨ₂−Ｐｈ−Ｐｈ−ＣＨ₂−で表される２価の基、水素添加ビスフェノールＡ残基、水素添加ビスフェノールＦ残基、水素添加ビスフェノールＡＤ残基、水素添加ビスフェノールＺ残基、シクロヘキサンジメタノール残基、トリシクロデカンジメタノール残基、テレフタル酸残基、イソフタル酸残基、ｏ−フタル酸残基などを挙げることができる。

(Wherein two R ²⁵ are the same or different alkyl groups having 1 to 5 carbon atoms, R ²⁶ is a divalent organic group having or not having an aromatic ring, and s is 0 or 1) Is shown.)
The dioxetane compound (A-2b ₀ ) represented by the formula is preferably used from the viewpoints of availability, reactivity, low hygroscopicity, mechanical properties of the cured product, and the like.
In the above general formula (A-2b ₀ ), examples of R ²⁵ include methyl, ethyl, propyl, butyl, and pentyl. Examples of R ²⁶ 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 Examples thereof include bisphenol AD residue, hydrogenated bisphenol Z residue, cyclohexanedimethanol residue, tricyclodecanedimethanol residue, terephthalic acid residue, isophthalic acid residue, o-phthalic acid residue and the like.

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

（式中、２個のＲ²⁷は互いに同じかまたは異なる炭素数１〜５のアルキル基、Ｒ²⁸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 ²⁷ represent the same or different alkyl group having 1 to 5 carbon atoms, and R ²⁸ represents a divalent organic group having or not having an aromatic ring.)

Specific examples of the dioxetane compound represented by the above formula (A-2b ₁ ) include bis (3-methyl-3-oxetanylmethyl) ether, bis (3-ethyl-3-oxetanylmethyl) ether, bis (3 -Propyl-3-oxetanylmethyl) ether, bis (3-butyl-3-oxetanylmethyl) ether, and the like.
Specific examples of the dioxetane compounds represented by the above formula (A-2b _{2), 2} pieces of R ²⁷ are both methyl in the above formula (A-2b _2), ethyl, propyl, butyl or pentyl group R ²⁸ is ethylene group, propylene group, butylene group, neopentylene group, n-pentamethylene group, n-hexamethylene group, etc.), formula: —CH ₂ —Ph—CH ₂ — or —CH ₂ —Ph—Ph A divalent group represented by —CH ₂ —, hydrogenated bisphenol A residue, hydrogenated bisphenol F residue, hydrogenated bisphenol AD residue, hydrogenated bisphenol Z residue, cyclohexanedimethanol residue, tricyclode The dioxetane compound which is a candimethanol residue, a terephthalic acid residue, an isophthalic acid residue, and an o-phthalic acid residue can be mentioned.
Among them, as the polyoxetane compound (A-2b ₀ ), in the above formula (A-2b ₁ ), bis (3-methyl-3-oxetanylmethyl) in which two R ²⁷ are both a methyl group or an ethyl group. ) Ether and / or bis (3-ethyl-3-oxetanylmethyl) ether are preferably used from the viewpoints of availability, low hygroscopicity, mechanical properties of the cured product, and the like. -Oxetanylmethyl) ether is more preferably used.

  The resin composition for optical three-dimensional model | molding of this invention is contained in the resin composition for optical three-dimensional model | molding from points, such as the photocuring performance of the resin composition for optical three-dimensional model | molding, and the modeling property improvement by low viscosity. Based on the total mass of the cationically polymerizable organic compound (A), the oxetane compound (A-2) is preferably contained in a proportion of 1 to 35% by mass, and more preferably in a proportion of 5 to 30% by mass. Preferably, it is contained in a proportion of 7 to 25% by mass.

  Representative examples of the radical polymerizable organic compound (B) include compounds having a (meth) acrylate group, unsaturated polyester compounds, allyl urethane compounds, polythiol compounds, and the like. 1 type (s) or 2 or more types can be used. Among them, a compound having at least one (meth) acryloyloxy group in one molecule is preferably used. Specific examples include a reaction product of an epoxy compound and (meth) acrylic acid, and a (meth) alcohol (meth) An acrylic ester, urethane (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate, etc. can be mentioned.

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

Examples of the (meth) acrylic acid esters of the alcohols described above include aromatic alcohols, aliphatic alcohols, alicyclic alcohols and / or their alkylene oxide adducts having at least one hydroxyl group in the molecule; Mention may be made of (meth) acrylates obtained by reaction with (meth) acrylic acid.
More specifically, for example, bisphenol compounds such as bisphenol A and bisphenol S, or di (meth) acrylates of bisphenol compounds such as bisphenol A and bisphenol S in which the benzene ring is substituted with an alkoxy group, 2-ethylhexyl (meta ) Acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isooctyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) ) Acrylate, benzyl (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, diethyleneglycol Rudi (meth) acrylate, triethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyalkylene glycol di (meth) acrylate [for example, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate , Polytetramethylene glycol di (meth) acrylate, etc.], trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. Poly (meth) acrylates of polyhydric alcohols having at least one hydroxyl group, polyhydric alcohols such as diols, triols, tetraols, hexaols, etc. , And the like (meth) acrylates of alkylene oxide adducts of Lumpur.

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

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

  In the resin composition for optical three-dimensional modeling, as part of the radical polymerizable organic compound (B), based on the mass of the radical polymerizable organic compound (B), polytetramethylene glycol di (meth) acrylate, polypropylene glycol When polyalkylene glycol di (meth) acrylate such as di (meth) acrylate and polyethylene glycol di (meth) acrylate is contained in an amount of 1 to 20% by mass, further 2 to 15% by mass, and particularly 3 to 10% by mass. The toughness of the three-dimensional model obtained from the optical three-dimensional model resin composition is improved. As the polyalkylene glycol di (meth) acrylate, a poly (alkylene glycol) di (meth) acrylate having a number average molecular weight of 300 to 1500, particularly 600 to 900, is preferably used. However, when there is too much content of polyalkylene glycol di (meth) acrylate, the heat-deformation temperature of the three-dimensional molded item obtained will become low, and heat resistance will fall.

  The resin composition for optical three-dimensional modeling of the present invention includes at least one aromatic sulfonium compound (C-1) represented by the following general formula (C-1) as the cationic polymerization initiator (C) and the following: At least one aromatic sulfonium compound (C-2) represented by the general formula (C-2).

［上記の一般式（Ｃ−１）および一般式（Ｃ−２）中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵およびＲ⁶は１価の有機基、Ｒｆはフルオロアルキル基、ｍは上記の一般式（Ｃ−１）における「カチオン［Ｓ⁺（Ｒ¹）（Ｒ²）（Ｒ³）］が有する陽イオン価と同じ数、ｎは１〜５の整数およびｐは上記の一般式（Ｃ−２）における「カチオン［Ｓ⁺（Ｒ⁴）（Ｒ⁵）（Ｒ⁶）］が有する陽イオン価と同じ数である。］

[In the above general formulas (C-1) and (C-2), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are monovalent organic groups, Rf is a fluoroalkyl group, m is the same number as the cation number of “cation [S ⁺ (R ¹ ) (R ² ) (R ³ )]” in the above general formula (C-1), n is an integer of 1 to 5, and p is the above In general formula (C-2), “the same number as the cation number of the cation [S ⁺ (R ⁴ ) (R ⁵ ) (R ⁶ )].”

The aromatic sulfonium compound (C-1) includes a cation represented by the formula: [S ⁺ (R ¹ ) (R ² ) (R ³ )] and a formula: [P ⁻ F _6-n (Rf) _n ]. Is an ion-bonded salt.
The aromatic sulfonium compound (C-2) has a cation represented by the formula: [S ⁺ (R ⁴ ) (R ⁵ ) (R ⁶ )] and an anion represented by the formula: [P ⁻ F ₆ ]. , An ion-bonded salt.

In the aromatic sulfonium compound (C-1) and the aromatic sulfonium compound (C-2), R ¹ , R ² and R ³ which are monovalent organic groups are each independently R ⁴ , R ⁵ and R ^6. A monovalent aromatic group which may have a substituent, a monovalent aliphatic group which may have a substituent, or a monovalent heterocyclic group which may have a substituent. Any of them may be used, and among these, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may each independently have a substituent bonded to an aromatic ring. One or more of bonds selected from —S— (thioether bond), —SO— (sulfoxide bond), —O— (ether bond) and —CO— (carbonyl bond) It is a monovalent aromatic group having or not having a catalytic activity, easy to obtain From the viewpoints of properties, handling properties, etc.

In the aromatic sulfonium compound (C-1), Rf is a fluoroalkyl group, preferably a fluoroalkyl group having 1 to 10 carbon atoms, more preferably a fluoroalkyl group having 1 to 8 carbon atoms, More preferably, it is a fluoroalkyl group having 1 to 4 carbon atoms. The catalytic activity of the aromatic sulfonium compound (C-1) is that Rf is a fluoroalkyl group in which 80% or more, more than 90%, and particularly 100% of the hydrogen atoms in the alkyl group are substituted with fluorine atoms. From the point of view, it is preferable.
But are not limited to, Examples of preferred _{Rf, CF 3 -, C 2} F 5 -, CF 3 CF 2 CF 2 -, (CF 3) 2 CF-, C 4 F 9 -, C 5 _{F 11 -, C 6 F 13} -, C 7 F 15 -, C 8 F 17 - and the like can be illustrated, in particular _{CF 3 -, C 2 F 5} -, CF 3 CF 2 CF 2 -, (CF 3 ) ₂ CF- and C ₄ F ₉ -are preferred.

In the aromatic sulfonium compound (C-1), n is preferably an integer of 1 to 5 from the viewpoint that the composition is rapidly cured and the physical properties of the three-dimensional structure obtained by photocuring are improved.
In the aromatic sulfonium compound (C-1), m is the same number as the cation number of the cation [S ⁺ (R ¹ ) (R ² ) (R ³ )].
In the aromatic sulfonium compound (C-2), p is the same number as the cation number of the cation [S ⁺ (R ⁴ ) (R ⁵ ) (R ⁶ )].

Although not limited, R ¹ , R ² , and R ³ in the above general formulas (C-1) and (C-2) are representative examples of R ⁴ , R ^5, and R ⁶ . Examples include groups represented by the following formulas << 1 >> to << 11 >>.

［式中、Ｒ⁷、Ｒ⁸、Ｒ⁹、Ｒ¹⁰、Ｒ¹¹、Ｒ¹²、Ｒ¹³、Ｒ¹⁴、Ｒ¹⁵、Ｒ¹⁶、Ｒ¹⁷およびＲ¹⁸は、それぞれ独立して、置換基を有していてもよいアルキル基またはアリール基であり、Ｘ¹、Ｘ²、Ｘ³、Ｘ⁴、Ｘ⁵、Ｘ⁶、Ｘ⁷、Ｘ⁸、Ｘ⁹、Ｘ¹⁰、Ｘ¹¹、Ｘ¹²、Ｘ¹³、Ｘ¹⁴、Ｘ¹⁵、Ｘ¹⁶、Ｘ¹⁷、Ｘ¹⁸、Ｘ¹⁹、Ｘ²⁰、Ｘ²¹およびＸ²²は、それぞれ独立して、アルキル基、アリール基、アルコキシ基、アリールオキシ基、ヒドロキシ（ポリ）アルキレンオキシ基、水酸基、シアノ基、ニトロ基およびハロゲン原子から選ばれる基であり、Ｚ¹、Ｚ²、Ｚ³およびＺ⁴は、それぞれ独立して、式：−Ｓ−、−ＳＯ−および−Ｏ−から選ばれる２価の基であり、それぞれ独立してｄ¹は０〜５の整数、ｄ²、ｄ³およびｄ⁴は０〜４の整数、ｄ⁵は０〜５の整数、ｄ⁶、ｄ⁷、ｄ⁸、ｄ⁹、ｄ¹⁰、ｄ¹¹、ｄ¹²、ｄ¹³、ｄ¹⁴、ｄ¹⁵およびｄ¹⁶は０〜４の整数、ｄ¹⁷は０〜５の整数、ｄ¹⁸は０〜４の整数、ｄ¹⁹は０〜５の整数、ｄ²⁰、ｄ²¹およびｄ²²は０〜５の整数である。］

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

More specifically, the group represented by the formula << 1 >> is not particularly limited, and examples thereof include a phenyl group substituted with a halogen atom such as a phenyl group, a chlorophenyl group, and a bromophenyl group, methyl Examples thereof include a phenyl group substituted with an alkyl group such as a phenyl group and an ethylphenyl group, and a hydroxyphenyl group.
Examples of the group represented by the formula << 2 >> include a naphthyl group, a halogen-substituted naphthyl group, an alkyl group-substituted naphthyl group, and a hydroxyl group-substituted naphthyl group.
Examples of the group represented by Formula << 3 >> include a biphenylyl group, a halogen-substituted biphenylyl group, an alkyl group-substituted biphenylyl group, and a hydroxyl group-substituted biphenylyl group.
Examples of the group represented by the formula << 4 >> include, for example, a methylcarbonylphenyl group, a benzoylphenyl group, a hydrogen atom of a benzene ring in these groups is a halogen atom such as chlorine or bromine, an alkyl group such as a methyl group or an ethyl group And a group substituted with a hydroxyl group.
Examples of the group represented by the formula << 5 >> include a methylcarbonylphenylthiophenyl group, a benzoylphenylthiophenyl group, a hydrogen atom of a benzene ring in these groups is a halogen atom such as chlorine or bromine, a methyl group or an ethyl group And a group substituted with an alkyl group, a hydroxyl group, and the like.
Examples of the group represented by the formula << 6 >> include a methylthiophenyl group, a phenylthiophenyl group, a naphthylthiophenyl group, a methoxyphenyl group, a phenoxyphenyl group, and a naphthoxyphenyl group. In the formula << 6 >>, R ⁹ is phenyl. A group or a methyl group and Z ¹ is —SO—, a hydrogen atom of an aromatic ring in these groups substituted by a halogen atom such as chlorine or bromine, an alkyl group such as a methyl group or an ethyl group, or a hydroxyl group And so on.
Examples of the group represented by the formula << 7 >> include a methylthiophenylthiophenyl group, a phenylthiophenylthiophenyl group, a naphthylthiophenylthiophenyl group, a methoxyphenylthiophenyl group, a phenoxyphenylthiophenyl group, and a naphthoxyphenylthio group. A phenyl group, a group in which R ¹⁰ is a phenyl group or a methyl group and Z ² is —SO— in the formula << 7 >>, a hydrogen atom of an aromatic ring in these groups is a halogen atom such as chlorine or bromine, a methyl group or an ethyl group And a group substituted with an alkyl group, a hydroxyl group, and the like.

Examples of the group represented by the formula << 8 >> include a diphenylthiobiphenylyl group, a dinaphthylthiobiphenylyl group, a dimethylthiobiphenylyl group, and a hydrogen atom of an aromatic ring in these groups is a halogen atom such as chlorine or bromine. And a group substituted by an alkyl group such as a methyl group or an ethyl group, a hydroxyl group, or the like.
Examples of the group represented by the formula “9” include a group in which Z ³ and Z ⁴ are —S— in the formula “9”, a group in which Z ³ and Z ⁴ are —SO— in the formula “9”, Examples thereof include a group in which the hydrogen atom of the benzene ring in these groups is substituted by a halogen atom such as chlorine or bromine, an alkyl group such as a methyl group or an ethyl group, or a hydroxyl group.
Examples of the group represented by the formula << 10 >> include trialkylsilylphenyl groups such as trimethylsilylphenyl group and triethylsilylphenyl group, dialkylphenylsilylphenyl groups such as triphenylsilylphenyl group and dimethylphenylsilylphenyl group, and methyl. Examples include alkyldiphenylsilylphenyl groups such as diphenylsilylphenyl groups, groups in which the hydrogen atoms of the benzene ring in these groups are substituted by halogen atoms such as chlorine and bromine, alkyl groups such as methyl and ethyl groups, and hydroxyl groups. be able to.
Examples of the group represented by the formula << 11 >> include trialkylsilylphenylthiophenyl groups such as trimethylsilylphenylthiophenyl group and triethylsilylphenylthiophenyl group, triphenylsilylphenylthiophenyl group, and dimethylphenylsilylphenylthiophenyl group. Dialkylphenylsilylphenylthiophenyl groups such as alkyldiphenylsilylphenylthiophenyl groups such as methyldiphenylsilylphenylthiophenyl groups, hydrogen atoms of the benzene ring in these groups are halogen atoms such as chlorine and bromine, methyl groups and ethyl Examples thereof include an alkyl group such as a group, a group substituted with a hydroxyl group, and the like.

All of the ^six groups R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be different from each other, or two of the 6 groups are the same and the remaining 4 One group may be different from each other, three of the six groups may be the same and the remaining three groups may be different from each other, or four of the six groups may be the same And the remaining two groups may be different from each other, five of the six groups may be the same and the remaining one group may be different from each other, or all of the six groups may be The same group may be sufficient.
Without limitation, the cation [S ⁺ (R ¹ ) (R ² ) (R ³ )] in the aromatic sulfonium compound (C-1) and the cation [S ⁺ in the aromatic sulfonium compound (C-2) Examples of (R ⁴ ) (R ⁵ ) (R ⁶ )] include the following cations <a-1> to (a-20).

［式中、halは塩素原子またはフッ素原子、ｆは０または１であり、１つのカチオン基中に記載されている複数の置換基（hal)_fにおける各置換基の数ｆは各置換基（hal)_fごとに独立して０または１である。］

[Wherein, hal is a chlorine atom or a fluorine atom, f is 0 or 1, and the number f of each substituent in a plurality of substituents (hal) _f described in one cationic group is the number of each substituent ( hal) 0 or 1 independently for each _f . ]

［式中、halは塩素原子またはフッ素原子、ｆは０または１であり、１つのカチオン基中に記載されている複数の置換基（hal)_fにおける各置換基の数ｆは各置換基（hal)_fごとに独立して０または１である。］

[Wherein, hal is a chlorine atom or a fluorine atom, f is 0 or 1, and the number f of each substituent in a plurality of substituents (hal) _f described in one cationic group is the number of each substituent ( hal) 0 or 1 independently for each _f . ]

Further, specific examples of the anion represented by the formula: [P ^- F _6-n (Rf) _n ] in the aromatic sulfonium compound (C-1) include the following anions (b-1) to (b-11). ).

Although not limited at all, as a specific example of the aromatic sulfonium compound (C-1) that can be used in the present invention,
<1> Compound in which cation (a-1) and anion (b-1) are ion-bonded, compound in which cation (a-1) and anion (b-2) are ion-bonded, cation (a-1) and anion ( b-3) ion-bonded compound, cation (a-1) and anion (b-4) ion-bonded compound, cation (a-1) and anion (b-5) ion-bonded compound, cation ( a-1) anion (b-6) ion-bonded compound, cation (a-1) and anion (b-7) ion-bonded compound, cation (a-1) and anion (b-8) Ion-bonded compound, cation (a-1) and anion (b-9) ion-bonded compound, cation (a-1) and anion (b-10) ion-bonded compound, cation (a-1) and Anion (b-11 ) Is an ion-bonded compound;
<2> Compound in which cation (a-2) and anion (b-1) are ion-bonded, compound in which cation (a-2) and anion (b-2) are ion-bonded, cation (a-2) and anion ( b-3) ion-bonded compound, cation (a-2) and anion (b-4) ion-bonded compound, cation (a-2) and anion (b-5) ion-bonded compound, cation ( a-2) and anion (b-6) ion-bonded compound, cation (a-2) and anion (b-7) ion-bonded compound, cation (a-2) and anion (b-8) Ion-bonded compound, cation (a-2) and anion (b-9) ion-bonded compound, cation (a-2) and anion (b-10) ion-bonded compound, cation (a-2) and Anion (b-11 ) Is an ion-bonded compound;
<3> Compound in which cation (a-3) and anion (b-1) are ion-bonded, compound in which cation (a-3) and anion (b-2) are ion-bonded, cation (a-3) and anion ( b-3) ion-bonded compound, cation (a-3) and anion (b-4) ion-bonded compound, cation (a-3) and anion (b-5) ion-bonded compound, cation ( a-3) and anion (b-6) ion-bonded compound, cation (a-3) and anion (b-7) ion-bonded compound, cation (a-3) and anion (b-8) Ion-bonded compound, cation (a-3) and anion (b-9) ion-bonded compound, cation (a-3) and anion (b-10) ion-bonded compound, cation (a-3) and Anion (b-11 ) Is an ion-bonded compound;
<4> Compound in which cation (a-4) and anion (b-1) are ion-bonded, compound in which cation (a-4) and anion (b-2) are ion-bonded, cation (a-4) and anion ( b-3) ion-bonded compound, cation (a-4) and anion (b-4) ion-bonded compound, cation (a-4) and anion (b-5) ion-bonded compound, cation ( a-4) and anion (b-6) ion-bonded compound, cation (a-4) and anion (b-7) ion-bonded compound, cation (a-4) and anion (b-8) Ion-bonded compound, cation (a-4) and anion (b-9) ion-bonded compound, cation (a-4) and anion (b-10) ion-bonded compound, cation (a-4) and Anion (b-11 ) Is an ion-bonded compound;
<5> A compound in which a cation (a-5) and an anion (b-1) are ion-bonded, a compound in which a cation (a-5) and an anion (b-2) are ion-bonded, a cation (a-5) and an anion ( b-3) ion-bonded compound, cation (a-5) and anion (b-4) ion-bonded compound, cation (a-5) and anion (b-5) ion-bonded compound, cation ( a-5) and anion (b-6) ion-bonded compound, cation (a-5) and anion (b-7) ion-bonded compound, cation (a-5) and anion (b-8) Ion-bonded compound, cation (a-5) and anion (b-9) ion-bonded compound, cation (a-5) and anion (b-10) ion-bonded compound, cation (a-5) Anion (b-11 ) Is an ion-bonded compound;
<6> Compound in which cation (a-6) and anion (b-1) are ion-bonded, compound in which cation (a-6) and anion (b-2) are ion-bonded, cation (a-6) and anion ( b-3) ion-bonded compound, cation (a-6) and anion (b-4) ion-bonded compound, cation (a-6) and anion (b-5) ion-bonded compound, cation ( a-6) and anion (b-6) ion-bonded compound, cation (a-6) and anion (b-7) ion-bonded compound, cation (a-6) and anion (b-8) Ion-bonded compound, cation (a-6) and anion (b-9) ion-bonded compound, cation (a-6) and anion (b-10) ion-bonded compound, cation (a-6) and Anion (b-11 ) Is an ion-bonded compound;
<7> A compound in which a cation (a-7) and an anion (b-1) are ion-bonded, a compound in which a cation (a-7) and an anion (b-2) are ion-bonded, a cation (a-7) and an anion ( b-3) ion-bonded compound, cation (a-7) and anion (b-4) ion-bonded compound, cation (a-7) and anion (b-5) ion-bonded compound, cation ( a-7) and anion (b-6) ion-bonded compound, cation (a-7) and anion (b-7) ion-bonded compound, cation (a-7) and anion (b-8) An ion-bonded compound, a compound in which a cation (a-7) and an anion (b-9) are ion-bonded, a compound in which a cation (a-7) and an anion (b-10) are ion-bonded, and a cation (a-7) Anion (b-11 ) Is an ion-bonded compound;
<8> A compound in which one cation (a-8) and two anions (b-1) are ion-bonded, a compound in which one cation (a-8) and two anions (b-2) are ion-bonded, a cation (A-8) a compound in which one anion (b-3) is ionically bonded, a compound in which one cation (a-8) and two anions (b-4) are ionically bonded, a cation (a-8) ) A compound in which one anion (b-5) is ionically bonded, a compound in which one cation (a-8) and two anions (b-6) are ionically bonded, one cation (a-8) A compound in which two anions (b-7) are ion-bonded, a compound in which one cation (a-8) and two anions (b-8) are ion-bonded, one cation (a-8) and an anion (b- 9) Two ion-bonded compounds, one cation (a-8) and anio A compound in which two ions (b-10) are ionically bonded, a compound in which one cation (a-8) and two anions (b-11) are ionically bonded;
<9> Compound in which cation (a-9) and anion (b-1) are ion-bonded, compound in which cation (a-9) and anion (b-2) are ion-bonded, cation (a-9) and anion ( b-3) ion-bonded compound, cation (a-9) and anion (b-4) ion-bonded compound, cation (a-9) and anion (b-5) ion-bonded compound, cation ( a-9) and anion (b-6) ion-bonded compound, cation (a-9) and anion (b-7) ion-bonded compound, cation (a-9) and anion (b-8) Ion-bonded compound, cation (a-9) and anion (b-9) ion-bonded compound, cation (a-9) and anion (b-10) ion-bonded compound, cation (a-9) and Anion (b-11 ) Is an ion-bonded compound;
<10> Compound in which cation (a-10) and anion (b-1) are ion-bonded, compound in which cation (a-10) and anion (b-2) are ion-bonded, cation (a-10) and anion ( b-3) ion-bonded compound, cation (a-10) and anion (b-4) ion-bonded compound, cation (a-10) and anion (b-5) ion-bonded compound, cation ( a-10) and anion (b-6) ion-bonded compound, cation (a-10) and anion (b-7) ion-bonded compound, cation (a-10) and anion (b-8) Ion-bonded compound, cation (a-10) and anion (b-9) ion-bonded compound, cation (a-10) and anion (b-10) ion-bonded compound, cation (a-1 0) and an anion (b-11) are ion-bonded compounds;
And so on.

Specific examples of the aromatic sulfonium compound (C-1) that can be used in the present invention include:
<11> Compound in which cation (a-11) and anion (b-1) are ion-bonded, compound in which cation (a-11) and anion (b-2) are ion-bonded, cation (a-11) and anion ( b-3) ion-bonded compound, cation (a-11) and anion (b-4) ion-bonded compound, cation (a-11) and anion (b-5) ion-bonded compound, cation ( a-11) and anion (b-6) ion-bonded compound, cation (a-11) and anion (b-7) ion-bonded compound, cation (a-11) and anion (b-8) Ion-bonded compound, cation (a-11) and anion (b-9) ion-bonded compound, cation (a-11) and anion (b-10) ion-bonded compound, cation (a-1 1) a compound in which an anion (b-11) is ion-bonded;
<12> Compound in which cation (a-12) and anion (b-1) are ion-bonded, compound in which cation (a-12) and anion (b-2) are ion-bonded, cation (a-12) and anion ( b-3) ion-bonded compound, cation (a-12) and anion (b-4) ion-bonded compound, cation (a-12) and anion (b-5) ion-bonded compound, cation ( a-12) and anion (b-6) ion-bonded compound, cation (a-12) and anion (b-7) ion-bonded compound, cation (a-12) and anion (b-8) Ion-bonded compound, cation (a-12) and anion (b-9) ion-bonded compound, cation (a-12) and anion (b-10) ion-bonded compound, cation (a-1 2) a compound in which an anion (b-11) is ion-bonded;
<13> Compound in which cation (a-13) and anion (b-1) are ion-bonded, compound in which cation (a-13) and anion (b-2) are ion-bonded, cation (a-13) and anion ( b-3) ion-bonded compound, cation (a-13) and anion (b-4) ion-bonded compound, cation (a-13) and anion (b-5) ion-bonded compound, cation ( a-13) and anion (b-6) ion-bonded compound, cation (a-13) and anion (b-7) ion-bonded compound, cation (a-13) and anion (b-8) An ion-bonded compound, a compound in which a cation (a-13) and an anion (b-9) are ion-bonded, a compound in which a cation (a-13) and an anion (b-10) are ion-bonded, a cation (a-1 3) a compound in which anion (b-11) is ion-bonded;
<14> A compound in which one cation (a-14) and two anions (b-1) are ion-bonded, a compound in which one cation (a-14) and two anions (b-2) are ion-bonded, a cation (A-14) a compound in which one anion (b-3) is ionically bonded, a compound in which one cation (a-14) and two anions (b-4) are ionically bonded, a cation (a-14) ) A compound in which one anion (b-5) is ionically bonded, a compound in which one cation (a-14) and two anions (b-6) are ionically bonded, one cation (a-14) A compound in which two anions (b-7) are ion-bonded, a compound in which one cation (a-14) and two anions (b-8) are ion-bonded, one cation (a-14) and an anion (b- 9) Two ion-bonded compounds, cations ( a-14) a compound in which one anion (b-10) is ionically bonded, a compound in which one cation (a-14) and an anion (b-112) are ionically bonded;
<15> Compound in which cation (a-15) and anion (b-1) are ion-bonded, compound in which cation (a-15) and anion (b-2) are ion-bonded, cation (a-15) and anion ( b-3) ion-bonded compound, cation (a-15) and anion (b-4) ion-bonded compound, cation (a-15) and anion (b-5) ion-bonded compound, cation ( a-15) and anion (b-6) ion-bonded compound, cation (a-15) and anion (b-7) ion-bonded compound, cation (a-15) and anion (b-8) An ion-bonded compound, a compound in which a cation (a-15) and an anion (b-9) are ion-bonded, a compound in which a cation (a-15) and an anion (b-10) are ion-bonded, a cation (a-1 5) a compound in which anion (b-11) is ion-bonded;
<16> Compound in which cation (a-16) and anion (b-1) are ion-bonded, compound in which cation (a-16) and anion (b-2) are ion-bonded, cation (a-16) and anion ( b-3) ion-bonded compound, cation (a-16) and anion (b-4) ion-bonded compound, cation (a-16) and anion (b-5) ion-bonded compound, cation ( a-16) and anion (b-6) ion-bonded compound, cation (a-16) and anion (b-7) ion-bonded compound, cation (a-16) and anion (b-8) An ion-bonded compound, a compound in which a cation (a-16) and an anion (b-9) are ion-bonded, a compound in which a cation (a-16) and an anion (b-10) are ion-bonded, a cation (a-1 6) a compound in which anion (b-11) is ion-bonded;
<17> Compound in which cation (a-17) and anion (b-1) are ion-bonded, compound in which cation (a-17) and anion (b-2) are ion-bonded, cation (a-17) and anion ( b-3) ion-bonded compound, cation (a-17) and anion (b-4) ion-bonded compound, cation (a-17) and anion (b-5) ion-bonded compound, cation ( a-17) and anion (b-6) ion-bonded compound, cation (a-17) and anion (b-7) ion-bonded compound, cation (a-17) and anion (b-8) Ion-bonded compound, cation (a-17) and anion (b-9) ion-bonded compound, cation (a-17) and anion (b-10) ion-bonded compound, cation (a-1 7) and an anion (b-11) ion-bonded compound;
<18> Compound in which cation (a-18) and anion (b-1) are ion-bonded, compound in which cation (a-18) and anion (b-2) are ion-bonded, cation (a-18) and anion ( b-3) ion-bonded compound, cation (a-18) and anion (b-4) ion-bonded compound, cation (a-18) and anion (b-5) ion-bonded compound, cation ( a-18) and anion (b-6) ion-bonded compound, cation (a-18) and anion (b-7) ion-bonded compound, cation (a-18) and anion (b-8) An ion-bonded compound, a compound in which a cation (a-18) and an anion (b-9) are ion-bonded, a compound in which a cation (a-18) and an anion (b-10) are ion-bonded, a cation (a-1 8) a compound in which anion (b-11) is ionically bonded;
<19> Compound in which one cation (a-19) and two anions (b-1) are ion-bonded, Compound in which one cation (a-19) and two anions (b-2) are ion-bonded, cation (A-19) a compound in which one anion (b-3) is ionically bonded, a compound in which one cation (a-19) and two anions (b-4) are ionically bonded, a cation (a-19) ) A compound in which one anion (b-5) is ionically bonded, a compound in which one cation (a-19) and two anions (b-6) are ionically bonded, one cation (a-19) Compound in which two anions (b-7) are ion-bonded, compound in which one cation (a-19) and two anions (b-8) are ion-bonded, one cation (a-19) and anion (b- 9) Two ion-bonded compounds, cations ( a-19) a compound in which one anion (b-10) is ionically bonded, a compound in which one cation (a-19) and two anions (b-11) are ionically bonded;
<20> A compound in which a cation (a-20) and an anion (b-1) are ion-bonded, a compound in which a cation (a-20) and an anion (b-2) are ion-bonded, a cation (a-20) and an anion ( b-3) ion-bonded compound, cation (a-20) and anion (b-4) ion-bonded compound, cation (a-20) and anion (b-5) ion-bonded compound, cation ( a-20) and anion (b-6) ion-bonded compound, cation (a-20) and anion (b-7) ion-bonded compound, cation (a-20) and anion (b-8) Ion-bonded compound, cation (a-20) and anion (b-9) ion-bonded compound, cation (a-20) and anion (b-10) ion-bonded compound, cation (a-2 0) and an anion (b-11) are ion-bonded compounds;
And so on.

  In the present invention, as the aromatic sulfonium compound (C-1), only one kind of the above-described compounds may be used, or two or more kinds may be used in combination.

The cation [S ⁺ (R ⁴ ) (R ⁵ ) (R ⁶ )] in the aromatic sulfonium compound (C-2) is not limited in any way, but for example, the above cation <a-1> To (a-20).

The aromatic sulfonium compound (C-2) that can be used in the present invention is not limited. For example, any one of the above-described cations (a-1) to (a-20) and a positive A compound in which one or two of the anions represented by the formula [P ⁻ F ₆ ] are ion-bonded can be given depending on the ionic value (cationic value) of the ion (cation).

  In the present invention, as the aromatic sulfonium compound (C-2), only one type of compound included in the category of the compound represented by the general formula (C-2) may be used, or two or more types may be used. You may use together.

In the present invention, as the aromatic sulfonium compound (C-1), a cation (sulfonium ion) represented by the formula: [S ⁺ (R ¹ ) (R ² ) (R ³ )] and a formula: [PF ₃ (Rf) ₃ ] is used, and an aromatic sulfonium compound represented by the above general formula (C-2) is used as a compound in which an anion [trifluorotris (fluoroalkyl) phosphate ion] represented by the formula When (C-2) is used in combination, a three-dimensional structure having a high activity as a cationic polymerization initiator and a lower yellowness is obtained.
Preferable examples of the cation in the aromatic sulfonium compound (C-2) at that time include cations (a-4), (a-5), and (a-11).

The resin composition for optical three-dimensional model | molding of this invention uses an aromatic sulfonium compound (C-1) and an aromatic sulfonium compound (C-2) as an aromatic sulfonium compound (C-1) as a cationic polymerization initiator: The aromatic sulfonium compound (C-2) is preferably contained at a mass ratio of 90:10 to 60:40, more preferably 85:15 to 70:30.
By containing the aromatic sulfonium compound (C-1) and the aromatic sulfonium compound (C-2) at the above-described mass ratio, while maintaining high curing performance when irradiated with active energy rays such as light, etc. It is possible to produce a three-dimensional structure having a low yellowness and excellent colorless transparency. When the proportion of the aromatic sulfonium compound (C-1) is larger than the above-mentioned range [when the proportion of the aromatic sulfonium compound (C-2) is smaller than the above-mentioned range], the yellow coloring becomes large, while the aromatic When the proportion of the sulfonium compound (C-1) is less than the above range [when the proportion of the aromatic sulfonium compound (C-2) is more than the above range], the photocuring of the resin composition for optical three-dimensional modeling The performance tends to decrease.

  The production method of the aromatic sulfonium compound (C-1) and the aromatic sulfonium compound (C-2) used in the present invention is not particularly limited, and can be produced by, for example, the methods described in Patent Documents 4 and 5 and the like. it can. The aromatic sulfonium compound (C-1) and the aromatic sulfonium compound (C-2) are both commercially available, and the aromatic sulfonium compound (C-1) is available from San Apro Co., Ltd. from CPI-200K and CPI. The aromatic sulfonium compound (C-2) is available as CPI-100P, CPI-110P, CPI-500P, etc. from San Apro Co., Ltd. Among them, CPI-500K is preferably used as the aromatic sulfonium compound (C-1), and CPI-500P is preferably used as the aromatic sulfonium compound (C-2).

  The resin composition for optical three-dimensional model | molding of this invention is a polymerization start which can start radical polymerization of a radically polymerizable organic compound (B) when active energy rays, such as light, are irradiated as a radical polymerization initiator (D). Any of the agents can be used, and examples thereof include benzyl or its dialkyl acetal compound, phenyl ketone compound, acetophenone compound, benzoin or its alkyl ether compound, benzophenone compound, and thioxanthone compound.

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

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

In this invention, 1 type, or 2 or more types of radical polymerization initiator (D) can be mix | blended and used according to desired performance.
Among them, in the present invention, as the radical polymerization initiator (D), 1-hydroxycyclohexyl phenyl ketone is excellent in the strength and heat resistance of the three-dimensional structure obtained by stereolithography, and has good reactivity. It is preferably used from the viewpoint that the hue of the three-dimensional structure to be formed is good (eg, the yellowness is small).

The resin composition for optical three-dimensional model | molding of this invention is cation polymerizable organic compound (A) and radical polymerizable organic compound (B) from points, such as photocuring performance, modeling speed, and the dimensional stability of the three-dimensional model | molding obtained. ), A cationically polymerizable organic compound (A): a radically polymerizable organic compound (B) = 30: 70 to 90:10, further 50:50 to 85:15, particularly 60:40 to 80:20 in mass ratio. It is preferable to contain.
In the resin composition for optical three-dimensional modeling of the present invention, the cationic polymerization initiator (C) is 0.1 to 10% by mass, particularly 0.5 to 5%, based on the mass of the cationic polymerizable organic compound (A). The radical polymerization initiator (D) is contained in a proportion of 0.1 to 10% by mass, particularly 0.5 to 5% by mass, based on the mass of the radical polymerizable organic compound (B). It is preferable.

The resin composition for optical three-dimensional model | molding of this invention can contain the polyalkylene ether type compound depending on the case, and when it contains the polyalkylene ether type compound, the toughness of the three-dimensional modeled article obtained is improved. It is strong and difficult to break.
As the polyalkylene ether compound, a polyalkylene ether compound represented by the following general formula (E) is particularly preferably used.
^{Q-O- (R 20 -O-)} q- (R 21 -O-) r-Q '(E)
[Wherein, R ²⁰ and R ²¹ are linear or branched alkylene groups having 2 to 5 carbon atoms, and Q and Q ′ are each independently a hydrogen atom, an alkyl group, a phenyl group, an acetyl group, or benzoyl. And q and r each independently represent 0 or an integer of 1 or more (provided that both q and r cannot be 0 at the same time). ]

In the polyalkylene ether compound represented by the above general formula (E) [hereinafter sometimes referred to as “polyalkylene ether compound (E)”], q and r are both integers of 1 or more, and q and r Are 3 or more, oxyalkylene units (alkylene ether units): —R ²⁰ —O— and oxyalkyne units (alkylene ether units): —R ²¹ —O— are bonded randomly. Alternatively, they may be combined in a block shape, or random bonds and block bonds may be mixed.

In the polyalkylene ether compound (E), specific examples of R ²⁰ and R ²¹ 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 ²⁰ and R ²¹ 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 (E), specific examples of Q and Q ′ 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 Q and Q ′, particularly both are hydrogen atoms. When at least one of Q and Q ′ is a hydrogen atom, when the resin composition for optical three-dimensional modeling containing the polyalkylene ether compound (E) is cured by irradiation with active energy rays, the polyalkylene ether type The hydroxyl groups at both ends of the compound (E) react with a cationically polymerizable organic compound, a radical polymerization initiator, etc., and the polyalkylene ether compound (E) is bonded in the cured resin. The characteristics are further improved.

In the polyalkylene ether compound (E), q and r, which indicate 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 (E) include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyethylene oxide-polypropylene oxide block copolymer, random copolymer of ethylene oxide and propylene oxide, formula : Having an alkyl substituent represented by —CH ₂ CH ₂ CH (R ²⁹ ) CH ₂ O— (wherein R ²⁹ is a lower alkyl group having 1 to 4 carbon atoms, preferably a methyl or ethyl group). Polyether having an oxytetramethylene unit (tetramethylene ether unit having an alkyl substituent) bonded thereto, the oxytetramethylene unit and the above formula: —CH ₂ CH ₂ CH (R ²⁹ ) CH ₂ O— (wherein R ²⁹ Is an alkyl represented by a lower alkyl group having 1 to 4 carbon atoms. Oxytetramethylene units having a substituent and the like polyethers randomly bonded. The island portion can be composed of one or more of the polyalkylene ether compounds described above. 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 ²⁹ ) CH ₂ O— (wherein R ²⁹ is preferably a polyether in which tetramethylene ether units having an alkyl substituent represented by a lower alkyl group are randomly bonded. In this 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 three-dimensional model | molding of this invention contains a polyalkylene ether type compound, content of a polyalkylene ether type compound is 0.5 with respect to the total mass of the resin composition for optical three-dimensional model | molding. It is preferable that it is -30 mass%, It is more preferable that it is 1-20 mass%, It is still more preferable that it is 1-15 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.

The resin composition for optical three-dimensional model | molding of this invention can further contain the at least 1 sort (s) of dye (F) chosen from a purple dye and a blue dye. The resin composition for optical three-dimensional modeling of the present invention may or may not contain at least one dye (F) selected from a purple dye and a blue dye, but is selected from a purple dye and a blue dye. By containing an appropriate small amount of at least one kind of dye (F), yellowness can be further reduced while maintaining high transparency of the three-dimensional structure obtained by stereolithography, and thereby colorless transparency. Can be obtained.
As the dye (F) selected from a purple dye and a blue dye, a purple dye and / or a blue dye that does not reduce the photocuring sensitivity of the resin composition for optical three-dimensional modeling and does not impair the transparency of the three-dimensional modeled product to be obtained. Any dye can be used, for example, methyl violet 10B, methyl violet 2B (crystal violet), purple dye I [1,3-dioxoindan-2-ylidene) (carboxymethyl) (hydroxyoxylatophosphinylmethyl) iminium ] Purple No. 401, Blue No. 1 (Brilliant Blue FCF), Blue No. 2 (Indigo Carmine), Patent Blue VI and the like.
The resin composition for optical three-dimensional modeling of the present invention may contain only a purple dye, may contain only a blue dye, or contains both a purple dye and a blue dye. Also good.
The content in the case of containing at least one dye (F) selected from a violet dye and a blue dye in the optical three-dimensional modeling resin composition is 0. 0 based on the mass of the optical three-dimensional modeling resin composition. It is preferably 01 to 5 ppm, more preferably 0.05 to 3 ppm, and still more preferably 0.1 to 1 ppm. When there is too much content of dye (F), the color tone of the three-dimensional molded item obtained by optical modeling will become purple and it will become difficult to become colorless and transparent. In addition, when a violet pigment and / or a blue pigment is used instead of the dye (F) selected from a violet dye and a blue dye, the transparency of the three-dimensional structure decreases.

  As long as the effects of the present invention are not impaired, the resin composition for optical modeling according to the present invention includes an antifoaming agent, a leveling agent, a thickener, a flame retardant, an antioxidant, a modifying resin, and the like. One or two or more kinds may be contained in appropriate amounts.

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

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

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

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the examples.
In the following examples, the viscosity of the optical three-dimensional modeling resin composition, the mechanical characteristics of the optical modeling obtained by optical modeling using the optical modeling resin composition [tensile characteristics (tensile breaking strength, tensile breaking elongation, Degree, tensile elastic modulus), bending properties (bending strength, bending elastic modulus), impact strength], heat distortion temperature, yellowness and total light transmittance were measured 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) Tensile properties of optically shaped objects (tensile breaking strength, tensile breaking elongation, tensile elastic modulus):
Using the optical modeling thing (the dumbbell-shaped test piece based on JIS K-7113) produced in the following examples or comparative examples, according to JIS K-7113, the tensile breaking strength (tensile strength) of the test piece, the tensile strength The breaking elongation (tensile elongation) and tensile modulus were measured.

(3) Bending characteristics (bending strength, bending elastic modulus) of the optically shaped object:
The bending strength and the flexural modulus of the test piece were measured according to JIS K-7171 using the optically shaped article (bar-shaped test piece conforming to JIS K-7171) produced in the following examples or comparative examples. .

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

(5) Thermal deformation temperature of stereolithography:
Using the stereolithography produced in the following examples or comparative examples (bar-shaped test piece in accordance with JIS K-7171), using “HDT Tester 6M-2” manufactured by Toyo Seiki Co., Ltd. Apply a load of .81 MPa and measure the thermal deformation temperature of the test piece in accordance with JIS K-7207 (Method A), then apply a load of 0.45 MPa to the test piece and apply it to JIS K-7207 (Method B). The heat distortion temperature of the test piece was measured in conformity.

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

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

Example 1
(1) 5.5 parts by mass of 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate (“Cel-2021P” manufactured by Daicel Corporation), hydrogenated bisphenol A diglycidyl ether (Nippon Nippon Chemical Co., Ltd.) 60 parts by mass of “HBE-100” manufactured by company, 7.5 parts by mass of 3-ethyl-3-hydroxymethyloxetane (“OXT101” manufactured by Toagosei Co., Ltd.), bis (3-ethyl-3-oxetanylmethyl) ether ( 12.5 parts by mass of “OXT221” manufactured by Toagosei Co., Ltd., 13 parts by mass of dipentaerythritol pentaacrylate (“A-9550W” manufactured by Shin-Nakamura Chemical Co., Ltd.), “NK” manufactured by Shin-Nakamura Chemical Co., Ltd. Ester-LA ") 10 parts by weight, bisphenol A diglycidyl ether 3 parts by mass of adduct of 2 mol of phosphoric acid (“VR-77” manufactured by Showa Denko KK), polytetramethylene glycol diacrylate (number average molecular weight 650) (“A-PTMG-65” manufactured by Shin-Nakamura Chemical Co., Ltd.) 1.5 parts by mass, 1.5 parts by mass of polytetramethylene ether glycol ("PTG-850SN" manufactured by Hodogaya Chemical Co., Ltd., number average molecular weight 801-890), "CPI-500K" [aromatic sulfonium manufactured by San Apro Co., Ltd. Cationic polymerization initiator solution corresponding to compound (C-1) and containing a compound represented by the following formula (C-1α ₁ ) at a concentration of 50% by mass] 1.5 parts by mass, “CPI” manufactured by San Apro Co., Ltd. -500P "[corresponding to an aromatic sulfonium compound (C-2), and containing a compound represented by the following formula (C-2β) at a concentration of 50% by mass Solution] 1.5 parts by mass and 2.5 parts by mass of 1-hydroxy-cyclohexyl phenyl ketone ("Irgacure-184" manufactured by BASF, radical polymerization initiator) are mixed well to prepare a resin composition for optical three-dimensional modeling. did. It was 232 mPa * s when the viscosity of this resin composition for optical three-dimensional modeling was measured by the above-mentioned method.

(2) Using the resin composition for optical three-dimensional modeling obtained in (1) above, a semiconductor laser (rated output 400 mW; wavelength) using an ultra-high-speed optical modeling system (“SOLIFORM 500” manufactured by Nabtesco Corporation) 355 nm; manufactured by Spectra Physics Co., Ltd.), under the condition of a liquid surface irradiation energy of 100 mJ / cm ² , a slice pitch (lamination thickness) of 0.10 mm, and an average modeling time of 2 minutes per layer, Test specimens for measuring physical properties (dumbbell-shaped specimens in accordance with JIS K-7113, bar-shaped specimens in accordance with JIS K-7171, and Izod impact test specimens in accordance with JIS K-7110) are prepared. and, ultraviolet obtained specimen (metal halide lamp, wavelength 365 nm, intensity 3.0 mW / cm ²⁾ post-cured to be irradiated 20 minutes It was.
Using the test piece after post-curing, the mechanical properties, heat distortion temperature, yellowness and total light transmittance were measured by the methods described above.
The results are shown in Table 1 below.

Example 2
(1) In Example 1 (1), methyl violet 10B (“Crystal Violet” manufactured by Wako Pure Chemical Industries, Ltd.) 3.0 × 10 ⁻⁵ parts by mass (based on the mass of the resin composition for optical three-dimensional modeling) In addition, a resin composition for optical three-dimensional modeling was prepared in the same manner as (1) of Example 1 except that 0.25 ppm) was further added. It was 226 mPa * s when the viscosity of the resin composition for optical three-dimensional modeling obtained by this was measured by the above-mentioned method.
(2) Using the resin composition for optical three-dimensional modeling obtained in (1) above, a test piece for measuring physical properties was prepared and post-cured in the same manner as (2) of Example 1.
The mechanical properties, heat distortion temperature, yellowness and total light transmittance of the post-cured test piece were measured by the methods described above.
The results are shown in Table 1 below.

Example 3
(1) Instead of 1.5 parts by mass of “CPI-500K” in (1) of Example 1, “CPI-200K” [phosphorus represented by the following formula (C-1α ₂ ) manufactured by San Apro Co., Ltd. Cationic polymerization initiator solution containing 50% by mass of aromatic aromatic sulfonium compound] Resin composition for optical three-dimensional modeling in the same manner as (1) of Example 1 except that 1.5 parts by mass was mixed. Was prepared. It was 240 mPa * s when the viscosity of the resin composition for optical three-dimensional modeling obtained by this was measured by the above-mentioned method.

(2) Using the resin composition for optical three-dimensional modeling obtained in (1) above, a test piece for measuring physical properties was prepared and post-cured in the same manner as (2) of Example 1.
The mechanical properties, heat distortion temperature, yellowness and total light transmittance of the post-cured test piece were measured by the methods described above.
The results are shown in Table 1 below.

<< Comparative Example 1 >>
(1) In the same manner as (1) of Example 1, except that, in (1) of Example 1, “CPI-500P” was not mixed and 2.0 parts by mass of “CPI-500K” was mixed. A resin composition for optical three-dimensional modeling was prepared. It was 234 mPa * s when the viscosity of the resin composition for optical three-dimensional modeling obtained by this was measured by the above-mentioned method.
(2) Using the resin composition for optical three-dimensional modeling obtained in (1) above, a test piece for measuring physical properties was prepared and post-cured in the same manner as (2) of Example 1.
The mechanical properties, heat distortion temperature, yellowness and total light transmittance of the post-cured test piece were measured by the methods described above.
The results are shown in Table 1 below.

<< Comparative Example 2 >>
(1) In the same manner as in (1) of Example 1, except that 2.0 parts by mass of “CPI-500P” was mixed without mixing “CPI-500K” in (1) of Example 1. A resin composition for optical three-dimensional modeling was prepared. It was 226 mPa * s when the viscosity of the resin composition for optical three-dimensional modeling obtained by this was measured by the above-mentioned method.
(2) Using the resin composition for optical three-dimensional modeling obtained in (1) above, a test piece for measuring physical properties was prepared and post-cured in the same manner as (2) of Example 1.
The mechanical properties, heat distortion temperature, yellowness and total light transmittance of the post-cured test piece were measured by the methods described above.
The results are shown in Table 1 below.

<< Comparative Example 3 >>
(1) Instead of “CPI-500K” and “CPI-500P” in (1) of Example 1, “CPI-200K” manufactured by San Apro Co., Ltd. used in Example 3 [the above formula (C-1α ₂ ) Cationic polymerization initiator solution containing a phosphorus-based aromatic sulfonium compound represented by 50) in a concentration of 50% by mass], except that 2.0 parts by mass was mixed. A three-dimensional modeling resin composition was prepared. It was 242 mPa * s when the viscosity of the resin composition for optical three-dimensional modeling obtained by this was measured by the above-mentioned method.
(2) Using the resin composition for optical three-dimensional modeling obtained in (1) above, a test piece for measuring physical properties was prepared and post-cured in the same manner as (2) of Example 1.
The mechanical properties, heat distortion temperature, yellowness and total light transmittance of the post-cured test piece were measured by the methods described above.
The results are shown in Table 1 below.

As seen in the results in Table 1 above, the optical three-dimensional modeling of Examples 1 to 3 containing both the aromatic sulfonium compound (C-1) and the aromatic sulfonium compound (C-2) as the cationic polymerization initiator. The three-dimensional structure obtained using the resin composition for optical use has a low yellowness, a high total light transmittance, excellent colorless transparency, and in particular, a resin for optical three-dimensional structure of Example 2 further containing a purple dye The three-dimensional structure obtained by using the composition has a very low yellowness of 1 while maintaining a high total light transmittance of 86%, and is extremely excellent in colorless transparency.
On the other hand, the three-dimensional molded object obtained from the resin composition for optical three-dimensional model | molding of the comparative examples 1 and 3 which contain an aromatic sulfonium compound (C-1) independently as a cationic polymerization initiator is Example 1-. 3 is significantly higher in yellowness than the three-dimensional modeled product obtained by using the optical three-dimensional modeled resin composition.
The three-dimensional model obtained from the resin composition for optical three-dimensional modeling of Comparative Example 2 containing the aromatic sulfonium compound (C-2) alone is the same as the resin composition for optical three-dimensional modeling of Example 1. Although the yellowness is only slightly higher than that of the three-dimensional structure obtained by using the resin composition for optical three-dimensional structure of Examples 1 to 3, the breaking strength, bending strength and flexural modulus of the three-dimensional structure are Compared to the three-dimensional modeled object obtained by using the three-dimensional model, it is too soft and soft, and when manufacturing a three-dimensional modeled object with a complicated shape, it is easy to hang from the support and deform, and the three-dimensional modeled object has the desired shape and structure. It is difficult to manufacture things.

  It does not contain a toxic antimony cationic polymerization initiator, and as the cationic polymerization initiator (C), an aromatic sulfonium compound (C-1) and an aromatic sulfonium compound (C-2) which are phosphorus aromatic sulfonium salts ), The resin composition for optical three-dimensional modeling of the present invention is excellent in safety and handleability, and gives a three-dimensional modeled article having excellent transparency and colorless transparency. It is extremely useful as a resin composition.

Claims (12)

A resin composition for optical three-dimensional modeling, comprising a cationically polymerizable organic compound (A), a radically polymerizable organic compound (B), a cationic polymerization initiator (C) and a radical polymerization initiator (D), wherein the cationic polymerization As the initiator (C), at least one aromatic sulfonium compound (C-1) represented by the following general formula (C-1) and an aromatic represented by the following general formula (C-2) A resin composition for optical three-dimensional modeling, comprising at least one sulfonium compound.

[In the above general formulas (C-1) and (C-2), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are monovalent organic groups, Rf is a fluoroalkyl group, m is the same number as the cation number of “cation [S ⁺ (R ¹ ) (R ² ) (R ³ )]” in the above general formula (C-1), n is an integer of 1 to 5, and p is the above In general formula (C-2), “the same number as the cation number of the cation [S ⁺ (R ⁴ ) (R ⁵ ) (R ⁶ )].”   The resin composition for optical three-dimensional modeling according to claim 1, wherein a content ratio of the aromatic sulfonium compound (C-1): the aromatic sulfonium compound (C-2) is a mass ratio of 90:10 to 60:40. .   The resin for optical three-dimensional modeling according to claim 1 or 2, wherein the content ratio of the aromatic sulfonium compound (C-1): the aromatic sulfonium compound (C-2) is a mass ratio of 85:15 to 70:30. Composition. R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ in the above general formula (C-1) and general formula (C-2) are each independently a substituent bonded to an aromatic ring. Is a monovalent aromatic group which may have one or more bonds represented by the formulas: —S—, —SO—, —O— and —CO— Or it is a monovalent | monohydric aromatic group which does not have, The resin composition for optical three-dimensional model | molding of any one of Claims 1-3. R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ in the general formula (C-1) and the general formula (C-2) are each independently represented by the following general formula << 1 >> The resin composition for optical three-dimensional modeling according to any one of claims 1 to 4, which is any group represented by << 11 >>.

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

Wherein R ¹⁹ is hydrogenated bisphenol A residue, hydrogenated bisphenol E residue, hydrogenated bisphenol F residue, hydrogenated bisphenol AD residue, hydrogenated bisphenol Z residue, cyclohexanedimethanol residue or trimethyl Cyclodecanedimethanol residue is shown.)
The alicyclic diglycidyl ether compound (A-1) represented by formula (A-1) is contained in a proportion of 50 to 100% by mass based on the total mass of the cationically polymerizable organic compound (A). 2. The resin composition for optical three-dimensional modeling according to item 1.   The optical three-dimensional model | molding of any one of Claims 1-6 which contains an oxetane compound (A-2) in the ratio of 1-35 mass% based on the mass of a cationically polymerizable organic compound (A). Resin composition.   The optical three-dimensional structure according to any one of claims 1 to 7, wherein the polyalkylene glycol di (meth) acrylate is contained in a proportion of 1 to 20% by mass based on the mass of the radical polymerizable organic compound (B). Resin composition for modeling.   The content ratio of the cationic polymerizable organic compound (A): radical polymerizable organic compound (B) is 30:70 to 90:10 (mass ratio), and the cationic polymerization initiator (C) is changed to the cationic polymerizable organic compound (A). ) Based on the mass of the radical polymerizable initiator (D) in a proportion of 0.1 to 10% by mass based on the mass of the radical polymerizable organic compound (B). The resin composition for optical three-dimensional model | molding of any one of Claims 1-8 to contain. The following general formula (E);
^{Q-O- (R 20 -O-)} q- (R 21 -O-) r-Q '(E)
[Wherein, R ²⁰ and R ²¹ are linear or branched alkylene groups having 2 to 5 carbon atoms, and Q and Q ′ are each independently a hydrogen atom, an alkyl group, a phenyl group, an acetyl group, or benzoyl. And q and r each independently represent 0 or an integer of 1 or more (provided that both q and r cannot be 0 at the same time). ]
The polyalkylene ether type compound (E) represented by any one of Claims 1-9 which further contains in the ratio of 0.5-30 mass% based on the total mass of the resin composition for optical three-dimensional modeling. 2. The resin composition for optical three-dimensional modeling according to item 1.   The at least 1 sort (s) of dyes (F) chosen from a purple dye and a blue dye are further contained in the quantity of 0.01-10 ppm based on the total mass of the resin composition for optical three-dimensional modeling. The resin composition for optical three-dimensional modeling of any one of Claims 1.   The method of manufacturing a three-dimensional molded item by performing optical three-dimensional modeling using the resin composition for optical three-dimensional modeling of any one of Claims 1-11.