JP4969137B2 - Optical three-dimensional resin composition - Google Patents

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 using a non-antimony polymerization initiator that is excellent in safety and has no environmental pollution, and the resin composition for optical three-dimensional modeling of the present invention. By using an object, an optical three-dimensional object that is excellent in dimensional accuracy, modeling accuracy, dimensional stability, toughness, other mechanical properties, water resistance, and moisture resistance while preventing contamination of the global environment with high curing sensitivity. It can be manufactured safely and at a high molding speed with good productivity.

In recent years, a method for three-dimensional optical modeling of a liquid photocurable resin composition based on data input to a three-dimensional CAD has achieved good dimensional accuracy without producing a mold or the like. Have been widely adopted.
As a typical example of the optical three-dimensional modeling method, a predetermined thickness is obtained by selectively irradiating a computer-controlled ultraviolet ray so that a desired pattern is obtained on the liquid surface of the liquid photocurable resin placed in a container. Finally, a one-layer liquid resin is supplied onto the cured layer, and similarly cured by irradiation with ultraviolet rays in the same manner as described above, and finally a three-dimensional structure is obtained by repeating the lamination operation to obtain a continuous cured layer. The method of obtaining can be mentioned. With this optical three-dimensional modeling method, it is possible to easily obtain a model having a considerably complicated shape in a relatively short time.

  The resin or resin composition used for optical three-dimensional modeling has high curing sensitivity with active energy rays, low viscosity and excellent handling at the time of molding, and less absorption of moisture and moisture over time, lowering of curing sensitivity There is no problem, the resolution of the molded object is high and the modeling accuracy is excellent, the volumetric shrinkage ratio at the time of curing is small, and the molded object obtained by curing has mechanical properties, durability, water resistance, moisture resistance, heat resistance Various characteristics such as excellent properties are required.

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

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

  Photocationic polymerization initiators for photopolymerizing cationically polymerizable organic compounds include aromatic sulfonium salts of Group VIIa elements (see Patent Document 2), aromatic onium salts of Group VIa elements (see Patent Document 3) ), Photocationic polymerization initiators made of an aromatic onium salt of a Group Va element (see Patent Document 4) and the like are known. Among them, in the photocurable resin composition containing a cationically polymerizable organic compound, a sulfonium salt containing antimony is widely used as a photocationic polymerization initiator, and a typical example thereof is represented by the following formula (IIIa). Or a mixture of a compound represented by the formula (IIIa) and a compound represented by the formula (IIIb).

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. In view of this, it has a photopolymerization initiating ability comparable to or surpassing that of antimony-based photocationic polymerization initiators that have been widely used in the past, has low toxicity, is excellent in safety and handling, and is suitable for work environments and the earth. There has been a demand for a resin composition for optical three-dimensional modeling containing a photocationic polymerization initiator that does not cause environmental pollution.
In addition, with the expansion of applications of optical modeling objects, it is possible to smoothly manufacture optical modeling objects with excellent dimensional stability and high dimensional accuracy, and further excellent toughness, and external stress such as bending is applied. However, there is a demand for a resin composition for optical three-dimensional modeling that can form a three-dimensional model that is not easily damaged and has excellent durability.

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

An object of the present invention is to provide a resin composition for optical three-dimensional modeling that does not contain a toxic component such as an antimony compound, thereby being excellent in safety and handling, and causing no contamination of the work environment or the global environment. Is to provide.
Furthermore, the object of the present invention is excellent in safety, has high curing sensitivity by active energy rays, can produce a molded article with high productivity in a reduced active energy ray irradiation time, and is also dimensional stability. It is an object to provide a resin composition for optical three-dimensional modeling that is excellent, has high dimensional accuracy, and can smoothly produce an optical modeling object with small dimensional change even when left under high humidity.
The object of the present invention is excellent in toughness, excellent in durability without being damaged even when external stress such as impact and bending is applied, and further in dimensional accuracy, other mechanical properties, water resistance, moisture resistance It is to provide a resin composition for optical three-dimensional modeling that can form a three-dimensional molded product having excellent heat resistance.

  In order to solve the above-mentioned problems, the present inventors have intensively studied. As a result, in the resin composition for optical three-dimensional modeling containing an epoxy compound, a radical polymerizable organic compound, an active energy ray sensitive cationic polymerization initiator and an active energy ray sensitive radical polymerization initiator, a specific alicyclic ring is used as the epoxy compound. When the diglycidyl ether compound is used, the dimensional change is extremely small even when left under high humidity, the dimensional stability over time is improved, and the desired optically shaped object can be produced with high dimensional accuracy, and the activity Initiates photocationic polymerization of non-antimony aromatic sulfonium compounds with a fluorophosphate having a fluorinated alkyl group as a counter ion instead of the conventional sulfonium salt containing antimony as an energy ray-sensitive cationic polymerization initiator. When blended as an agent, in the resin composition for optical three-dimensional modeling The photocationic polymerization of the poxy compound is carried out smoothly, and a three-dimensional shaped product with excellent characteristics such as dimensional accuracy, mechanical properties, water resistance, moisture resistance, and heat resistance can be obtained with a shortened active energy ray irradiation time. The present inventors have found that the function as a photocationic polymerization initiator of the non-antimony aromatic sulfonium compound is not inferior to that of a sulfonium salt containing antimony that has been widely used conventionally.

  Furthermore, the present inventors include an oxetane compound in a specific ratio in the resin composition for optical three-dimensional modeling containing an epoxy compound and a photocationic polymerization initiator composed of a non-antimony aromatic sulfonium compound. It is excellent in toughness while curing the resin composition for optical three-dimensional modeling using active energy rays, and excellent in durability without being damaged even when external stress such as impact and bending is applied. In addition, it has been found that a three-dimensional structure excellent in dimensional accuracy, other mechanical properties, water resistance, moisture resistance, heat resistance, and the like can be obtained, and the present invention has been completed based on these findings.

That is, the present invention
(1) (i) An optical steric composition containing an epoxy compound (a), a radical polymerizable organic compound (b), an active energy ray sensitive cationic polymerization initiator (c) and an active energy ray sensitive radical polymerization initiator (d) A resin composition for modeling;
(Ii) (ii) The epoxy compound (a) is represented by the following general formula (I);

（式中、Ｒ^aは、水素添加ビスフェノールＡ残基、水素添加ビスフェノールＦ残基、水素添加ビスフェノールＺ残基、シクロヘキサンジメタノール残基またはトリシクロデカンジメタノール残基を示す。）
で表される脂環式ジグリシジルエーテル化合物を、エポキシ化合物（ａ）の全質量に基づいて３０〜１００質量％の割合で含有するエポキシ化合物であり；
（iii） 活性エネルギー線感受性カチオン重合開始剤（ｃ）が、下記の一般式（II）；

(In the formula, ^Ra represents a hydrogenated bisphenol A residue, a hydrogenated bisphenol F residue, a hydrogenated bisphenol Z residue, a cyclohexanedimethanol residue, or a tricyclodecanedimethanol residue.)
An alicyclic diglycidyl ether compound represented by the formula (a) based on the total mass of the epoxy compound (a) in an amount of 30 to 100% by mass;
(Iii) The active energy ray-sensitive cationic polymerization initiator (c) is represented by the following general formula (II):

［上記の式（Ｉ）中、Ｒ¹およびＲ²はそれぞれ独立して下記の式（ｉ）〜（iv）；

[In the above formula (I), R ¹ and R ² are each independently the following formulas (i) to (iv);

｛式（ii）および式（iv）中、Ｘは塩素原子またはフッ素原子を示す｝
で表される基のいずれかであり、Ｒ³は下記の式（ｖ）；

{In Formula (ii) and Formula (iv), X represents a chlorine atom or a fluorine atom}
R ³ is any one of the groups represented by the following formula (v);

で表される基であり、Ｒｆは炭素数１〜８のフルオロアルキル基であり、ａは０〜３の整数、ｂは０〜３の整数およびｃは０または１であって、ａとｂとｃの合計が３であり、ｍは１＋ｃと同じ数であり、ｎは１〜５の整数である。］
で表される芳香族スルホニウム化合物であり；且つ、
（iv） エポキシ化合物（ａ）１００質量部に対して、オキセタン化合物（ｅ）を５〜２００質量部の割合で含有する；
ことを特徴とする光学的立体造形用樹脂組成物である。

Rf is a fluoroalkyl group having 1 to 8 carbon atoms, a is an integer of 0 to 3, b is an integer of 0 to 3, and c is 0 or 1, and a and b And c is 3, m is the same number as 1 + c, and n is an integer of 1 to 5. ]
An aromatic sulfonium compound represented by :
(Iv) The oxetane compound (e) is contained at a ratio of 5 to 200 parts by mass with respect to 100 parts by mass of the epoxy compound (a);
The resin composition for optical three-dimensional modeling characterized by the above-mentioned.

And this invention,
(2) The aromatic sulfonium compound represented by the above general formula (II), wherein the content ratio of the epoxy compound (a): radically polymerizable organic compound (b) is 30:70 to 90:10 (mass ratio) In an amount of 0.1 to 10% by mass based on the mass of the epoxy compound (a), and the active energy ray-sensitive radical polymerization initiator (d) is 0 based on the mass of the radical polymerizable organic compound (b). The resin composition for optical three-dimensional modeling according to (1), which is contained at a ratio of 1 to 20% by mass; and
( 3 ) The method of manufacturing an optical three-dimensional molded item using the resin composition for optical three-dimensional modeling in any one of said (1) or (2) ;
It is.

The resin composition for optical three-dimensional modeling of the present invention (hereinafter sometimes referred to as “resin composition for optical modeling”) has a high curing sensitivity by active energy rays, and a target three-dimensional modeled object in a short modeling time. It can be manufactured with high productivity.
The resin composition for optical three-dimensional modeling of the present invention is excellent in dimensional stability, and is excellent in dimensional accuracy and high humidity by performing optical modeling using the resin composition for optical three-dimensional modeling of the present invention. Dimensional change is extremely small even when left on the surface, and the dimensional stability over time is good, and an optical three-dimensional modeled product that has excellent mechanical properties, water resistance, moisture resistance, heat resistance, etc. is smoothly produced. be able to.
In the resin composition for optical three-dimensional modeling of the present invention, since the non-antimony aromatic sulfonium compound (II) having low toxicity is used as the photocationic polymerization initiator, the safety and handling properties are excellent, and the work Does not cause pollution or deterioration of the environment or the global environment.
When the resin composition for optical three-dimensional modeling of the present invention containing an oxetane compound is used, in addition to the above-described properties, it is excellent in toughness and breaks even when external stress such as impact and bending is applied. It is difficult to smoothly produce a three-dimensional structure that is excellent in durability.

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

（式中、R^aは、水素添加ビスフェノールＡ残基、水素添加ビスフェノールＦ残基、水素添加ビスフェノールＺ残基、シクロヘキサンジメタノール残基またはトリシクロデカンジメタノール残基を示す。）
で表される脂環式ジグリシジルエーテル化合物［以下「脂環式ジグリシジルエーテル化合物（Ｉ）」という］を、エポキシ化合物（ａ）の全質量に基づいて１０〜１００質量％の割合で含有するエポキシ化合物を用いる。

(In the formula, ^Ra represents a hydrogenated bisphenol A residue, a hydrogenated bisphenol F residue, a hydrogenated bisphenol Z residue, a cyclohexanedimethanol residue or a tricyclodecanedimethanol residue.)
The alicyclic diglycidyl ether compound represented by the formula [hereinafter referred to as “alicyclic diglycidyl ether compound (I)”] is contained in a proportion of 10 to 100% by mass based on the total mass of the epoxy compound (a). An epoxy compound is used.

In the present invention, as the epoxy compound (a), the content of the alicyclic diglycidyl ether compound (I) is 10 to 100% by mass, so that the curing sensitivity, thick film curability, resolution, ultraviolet light The permeability and the like are further improved, the viscosity of the optical molding resin composition is lowered and the molding is smoothly performed, and the volumetric shrinkage of the optical molding obtained by the molding is further reduced. The
When the content ratio of the alicyclic diglycidyl ether compound (I) is less than 10% by mass based on the total mass of the epoxy compound (a), the dimensional stability of the modeled product under high humidity decreases.
As the epoxy compound (a), the content of the alicyclic diglycidyl ether compound (I) is 30 to 100% by mass, particularly 50 to 100% by mass, based on the total mass of the epoxy compound (a). It is preferable to use it, whereby the moisture resistance of the shaped object is improved and the change with time of the dimension is reduced.

  Specific examples of the alicyclic diglycidyl ether compound (I) used in the present invention include hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol Z diglycidyl ether, and cyclohexanedimethanol. Mention may be made of diglycidyl ether and tricyclodecane dimethanol diglycidyl ether. In the present invention, as the alicyclic diglycidyl ether compound (I), only one kind of the aforementioned diglycidyl ether may be used, or two or more kinds may be used in combination. Among them, as the alicyclic diglycidyl ether compound (I), hydrogenated bisphenol A diglycidyl ether and / or tricyclodecane dimethanol diglycidyl ether are preferable from the viewpoint of availability and moisture absorption resistance of a molded article. Used.

  Other epoxy compounds that may be used together with the alicyclic diglycidyl ether compound (I) as part of the epoxy compound (a) include an active energy ray-sensitive cationic polymerization initiator (hereinafter referred to as “cationic polymerization initiator”). Any epoxy compound that can be cationically polymerized in the presence of, for example, an alicyclic epoxy compound other than the alicyclic diglycidyl ether compound (I), an aliphatic epoxy compound, an aromatic epoxy compound, etc. Can be mentioned. As another epoxy compound, a polyepoxy compound having two or more epoxy groups in one molecule is more preferably used.

Examples of the other alicyclic epoxy compounds described above include polyglycidyl ethers of polyhydric alcohols having at least one alicyclic ring, or cyclohexene or cyclopentene ring-containing compounds such as hydrogen peroxide and peracid. Examples include cyclohexene oxide or cyclopentene oxide-containing compounds obtained by epoxidation with an oxidizing agent. More specifically, examples of the alicyclic epoxy 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-5,5-spiro-3 , 4-epoxy) cyclohexane-meta Oxane, bis (3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl carboxylate, dicyclopentadiene diepoxide, ethylene bis (3,4-epoxycyclohexanecarboxylate), epoxy hexahydrophthal Examples include dioctyl acid and di-2-ethylhexyl epoxyhexahydrophthalate.
Further, bis (3,4-epoxycyclohexyl) methane, 2,2-bis (3,4-epoxycyclohexyl) propane, 1,1-bis (3,4-epoxycyclohexyl) ethane, and the like can be given.

  Examples of commercially available products that can be suitably used as the above-described alicyclic epoxy compounds include, for example, UVR-6100, UVR-6105, UVR-6110, UVR-6128, UVR-622 (above, manufactured by Dow), Celoxide 2021, and Celoxide. 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, Celoxide 2000, Celoxide 3000, Cyclomer A200, Cyclomer M100, Epolide GT-301, Epolide GT-302, Epolide GT-401, Epolide GT-403 (above, Daicel Chemical Industries) Co., Ltd.), KRM-2110, KRM-2199 (manufactured by Asahi Denka Co., Ltd.) and the like.

  The aliphatic epoxy compound described above that can be used as the epoxy 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, and aliphatic long chains. Examples thereof include polyglycidyl esters of 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, and the like. Typical specific compounds include, for example, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane diglycidyl ether, and trimethylolpropane. Glycidyl ethers of polyhydric alcohols such as triglycidyl ether of sorbitol, tetraglycidyl ether of sorbitol, hexaglycidyl ether of dipentaerythritol, diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, and also propylene, trimethylolpropane, glycerin Polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as Jill ethers, such as diglycidyl esters of aliphatic long chain dibasic acid. 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 and epoxidized polybutadiene.

  The aromatic epoxy compound is not particularly limited, and examples thereof include polyglycidyl ethers of polyhydric phenols or alkylene oxide adducts thereof. Specifically, for example, bisphenol A, bisphenol F, Or the glycidyl ether of the compound which added alkylene oxides, such as ethylene oxide and a propylene oxide, to these, the glycidyl ether of a novolak resin, etc. can be mentioned.

Examples of the aromatic epoxy compound include bisphenol A diglycidyl ether (commercially available products such as Epicoat 828 manufactured by Japan Epoxy Resin, EP-4800 manufactured by Asahi Denka Co., Ltd.), and bisphenol F diglycidyl ether (commercially available products). As Epicoat 807 manufactured by Japan Epoxy Resin Co., EP-4900 manufactured by Asahi Denka Co., Ltd.), propylene oxide-modified bisphenol A diglycidyl ether And EP-4000 manufactured by Asahi Denka Co., Ltd.) and phenol novolac type epoxy resins (commercially available products include N-730 and N-770 manufactured by Dainippon Ink & Chemicals, Inc. and YDPN638 manufactured by Tohto Kasei Co., Ltd.).
Moreover, as a commercial item of the said aliphatic epoxy compound, for example, EX-212, EX-313, EX-321, EX-411, EX-521, EX-614, EX-711, EX manufactured by Nagase Gemtech Co., Ltd. -811, EX-821, EX-851, EX-911, EX-941, EX-920, YH-300, PG-202, and PG-207 manufactured by Tohto Kasei.

  In the present invention, as a part of the epoxy compound (a), one or more of the above-described other epoxy compounds other than the alicyclic diglycidyl ether compound (I) is used in a proportion of 90% by mass or less. Can do. When other epoxy compounds other than the alicyclic diglycidyl ether compound (I) are used, other polyepoxy compounds having two or more epoxy groups in one molecule based on the total mass of the other epoxy compounds It is preferable to use what contains 30 mass% or more.

  In the resin composition for optical modeling according to the present invention, as the radical polymerizable organic compound (b), an active energy ray sensitive radical polymerization initiator (d) [hereinafter simply referred to as “radical polymerization initiator (d)” or “radical polymerization initiator”. In the presence of [], any organic compound that undergoes radical polymerization and / or crosslinking when irradiated with ultraviolet rays or other active energy rays can be used. Representative examples of the radical polymerizable organic compound (b) include (meth) acrylate compounds, unsaturated polyester compounds, polythiol compounds, etc., and these radical polymerizable organic compounds may be used alone, Or you may use 2 or more types together. Among them, in the present invention, an acrylic compound having at least one (meth) acryl group in one molecule is preferably used as the radical polymerizable organic compound (b). ) Reaction products with acrylic acid, (meth) acrylic esters of alcohols, polyester (meth) acrylates, polyether (meth) acrylates, (meth) acrylic esters of polyols, and the like.

  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 reaction products. Among the aforementioned (meth) acrylate reaction products, a (meth) acrylate reaction product obtained by a reaction between an aromatic epoxy compound and (meth) acrylic acid is preferably used, and specific examples thereof include bisphenol A. (Meth) acrylate, epoxy novolac resin obtained by reacting glycidyl ether obtained by reaction of a bisphenol compound such as bisphenol S or an alkylene oxide adduct thereof and an epoxidizing agent such as epichlorohydrin with (meth) acrylic acid And an epoxy (meth) acrylate reaction product obtained by reacting (meth) acrylic acid.

  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, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isooctyl (meth) Acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, diethylene glycol di (meth) ) Acrylate, triethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) a Relate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, alkylene oxide adducts of polyhydric alcohols such as diol, triol, tetraol, hexaol, etc. A (meth) acrylate etc. can be mentioned. Among them, as the (meth) acrylate of alcohols, (meth) acrylate having two or more (meth) acryl groups in one molecule obtained by reaction of polyhydric alcohol and (meth) acrylic acid is preferably used. It is done. Of the (meth) acrylate compounds described above, an acrylate compound is preferably used in view of the polymerization rate rather than a methacrylate compound.

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

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

で表される芳香族スルホニウム化合物［以下「芳香族スルホニウム化合物(II)」という］を含有する。
芳香族スルホニウム化合物（II）は、式：［Ｓ⁺（Ｒ¹）_a（Ｒ²）_b（Ｒ³）_c］で表されるカチオンと、式：［Ｐ^-Ｆ_6-n（Ｒｆ）_n］で表されるアニオンが、イオン結合した塩である。
芳香族スルホニウム化合物（II）において、Ｒ¹およびＲ²は、それぞれ独立して下記の式（ｉ）で表されるフェニル基、式（ii）で表される塩化フェニル基またはフルオロフェニル基、式（iii）で表される４−フェニルチオフェニル基或いは式（iv）で表される基［式（iv）中、Ｘは塩素原子またはフッ素原子を示す］である。

And an aromatic sulfonium compound represented by the following [hereinafter referred to as “aromatic sulfonium compound (II)”].
The aromatic sulfonium compound (II) includes a cation represented by the formula: [S ⁺ (R ¹ ) _a (R ² ) _b (R ³ ) _c ], and a formula: [P ⁻ F _6-n (Rf) _n. ] Is an ion-bonded salt.
In the aromatic sulfonium compound (II), R ¹ and R ² are each independently a phenyl group represented by the following formula (i), a phenyl chloride group or a fluorophenyl group represented by the formula (ii), a formula A 4-phenylthiophenyl group represented by (iii) or a group represented by formula (iv) [in the formula (iv), X represents a chlorine atom or a fluorine atom].

In the aromatic sulfonium compound (II), R ¹ and R ² may be the same or different.
In the aromatic sulfonium compound (II), R ³ is a 4′-diphenylsulfonio-4-phenylthiophenyl group represented by the following formula (v).

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

In the aromatic sulfonium compound (II), Rf is a C1-C8 fluoroalkyl group. Rf is a fluoroalkyl group in which some of the hydrogen atoms in the alkyl group having 1 to 8 carbon atoms are substituted with fluorine atoms, or all the hydrogen atoms in the alkyl group having 1 to 8 carbon atoms are substituted with fluorine atoms. Any of perfluoroalkyl groups may be used. Among them, Rf is preferably a perfluoroalkyl group in which all of the hydrogen atoms in the alkyl group having 1 to 8 carbon atoms are substituted with fluorine atoms, from the viewpoint of reactivity, and as a preferred specific example of 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, and CF _3- , C ₂ F _5- , CF ₃ CF ₂ CF _2- , (CF ₃ ) ₂ CF-, C ₄ F ₉ -are particularly preferable.

  In the aromatic sulfonium compound (II), n is an integer of 1 to 5, and n is preferably an integer of 1 to 4, particularly an integer of 2 to 3, from the viewpoint of anion stability. When n is an integer of 2 or more, two or more fluoroalkyl groups Rf may be the same or different.

In general formula (II), m is the same number as 1 + c.
In the general formula (II), when c is 0 and the cation of the aromatic sulfonium compound (II) does not have R ³ [group represented by the above formula (v)], m is 1. .
In the general formula (II), when c is 1 and the cation of the aromatic sulfonium compound (II) has one R ³ [group represented by the above formula (v)], the formula: [S ⁺ (R ¹ ) _a (R ² ) _b (R ³ ) _c ] is a divalent cation, and the divalent cation includes two anions: [P ⁻ F _6-n ( Rf) _n ] is ionically bonded (m = 2).

Although not limited, As a specific example of the cation represented by the formula: [S ⁺ (R ¹ ) _a (R ² ) _b (R ³ ) _c ] in the aromatic sulfonium compound (II), Cations (IIa ₁ ) to (IIa ₇ ) can be mentioned.

Specific examples of the anion represented by the formula: [P ⁻ F _6-n (Rf) _n ] in the aromatic sulfonium compound (II) are represented by the following (IIb ₁ ) to (IIb ₁₁ ). Anions can be mentioned.

  Specific examples of the aromatic sulfonium compound (II) preferably used in the present invention include any of the compounds represented by the following formulas (II-1) to (II-11) or the following formula (II): -2) and a mixture of the compound represented by the formula (II-9).

  The production method of the aromatic sulfonium compound (II) is not particularly limited. For example, sulfonium chloride represented by the following general formula (IVa) and lithium fluorophosphate represented by the following general formula (IVb) After mixing in a mixed solvent of ether and water, the ether layer is recovered, and the recovered ether layer can be washed with water. In that case, the sulfonium chloride represented by the general formula (IVa), which is a raw material to be used, can be produced, for example, by the method described in Patent Document 5, and the fluoro represented by the general formula (IVb). Lithium phosphate can be produced by the method described in Patent Document 6.

（上記の式中、Ｒ¹、Ｒ²、Ｒ³、Ｒｆは上記したのと同じ基であり、ａ、ｂ、ｃ、ｍおよびｎは上記したと同じ数を示す。）

(In the above formula, R ¹ , R ² , R ³ and Rf are the same groups as described above, and a, b, c, m and n represent the same numbers as described above.)

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

Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin normal butyl ether, and benzoin isobutyl ether.
Examples of the benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4′-bisdiethylaminobenzophenone, 4,4′-dichlorobenzophenone, and the like.
Examples of the thioxanthone compound include thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, and 2-isopropylthioxanthone.
In this invention, 1 type, or 2 or more types of radical polymerization initiator (d) can be mix | blended and used according to desired performance.

  In the resin composition for optical modeling of the present invention, the content ratio of epoxy compound (a): radical polymerizable organic compound (b) is 30:70 to 90:10 (mass ratio) from the viewpoint of modeling speed. Is more preferable, and 40:60 to 85:15 (mass ratio) is more preferable. Moreover, the resin composition for optical modeling of the present invention contains the aromatic sulfonium compound (II) in a proportion of 0.1 to 10% by mass, particularly 1 to 5% by mass, based on the mass of the epoxy compound (a). The active energy ray-sensitive radical polymerization initiator (d) is preferably contained in an amount of 0.1 to 20% by mass, particularly 1 to 10% by mass, based on the mass of the radical polymerizable organic compound (b). .

  The resin composition for optical modeling of the present invention is used for the purpose of improving the reaction rate, together with the above-described aromatic sulfonium compound (II), or the aromatic sulfonium compound (II) and a radical polymerization initiator. A sensitizer, for example, dialkoxyanthracene such as dibutoxyanthracene, thioxanthone and the like may be contained.

The resin composition for optical modeling according to the present invention further contains an oxetane compound (e) together with the above-described components. By containing the oxetane compound (e), the optically shaped product obtained from the resin composition for optical modeling of the present invention also has increased toughness, and is less likely to be damaged even when stress such as impact and bending is applied, and has durability. improves.
As the oxetane compound (e), any of a monooxetane compound having one oxetane group in one molecule and a polyoxetane compound having two or more oxetane groups in one molecule can be used. The resin composition for optical modeling of the present invention may contain only one or both of a monooxetane compound and a polyoxetane compound as the oxetane compound (e).

  As the monooxetane compound, any compound having one oxetane group in one molecule can be used, and among them, a monooxetane monoalcohol having one oxetane group and one alcoholic hydroxyl group in one molecule. Are preferably used from the viewpoints of reactivity and viscosity of the composition. In particular, among the monooxetane monoalcohol compounds, the following general formula (V):

（式中、Ｒ⁴はアルキル基、アリール基またはアラルキル基であり、ｐは１〜６の整数を示す。）
で表されるモノオキセタンモノアルコールが入手性の点から好ましく用いられ、特に上記の一般式（Ｖ）においてｐが１である下記の一般式（Ｖａ）；

(In the formula, R ⁴ represents an alkyl group, an aryl group or an aralkyl group, and p represents an integer of 1 to 6)
Monooxetane monoalcohol represented by the following general formula (Va) wherein p is 1 in the above general formula (V);

（式中、Ｒ⁴は上記と同じ基を示す。）
が、入手の容易性、高反応性、粘度が低く取扱性に優れるなどの点からより好ましく用いられる。

(Wherein R ⁴ represents the same group as described above.)
However, it is more preferably used from the viewpoints of easy availability, high reactivity, low viscosity and excellent handleability.

In the above general formulas (V) and (Va), examples of R ⁴ include methyl, ethyl, propyl, butyl, and pentyl.
Specific examples of the monooxetane monoalcohol represented by the general formula (Va) preferably used in the present invention include 3-hydroxymethyl-3-methyloxetane, 3-hydroxymethyl-3-ethyloxetane, 3-hydroxy Examples thereof include methyl-3-propyloxetane, 3-hydroxymethyl-3-normalbutyl oxetane, 3-hydroxymethyl-3-propyloxetane, and the like, and one or more of these can be used. Among these, 3-hydroxymethyl-3-methyloxetane and 3-hydroxymethyl-3-ethyloxetane are more preferably used from the viewpoints of easy availability and reactivity.

As the polyoxetane compound, a compound having two or more oxetane groups, for example, a compound having two, three or four oxetane groups can be used, and among them, a dioxetane compound having two oxetane groups is used. Preferably used.
In particular, as a dioxetane compound, the following general formula (VI):

（式中、２個のＲ⁵は互いに同じかまたは異なる炭素数１〜５のアルキル基、Ｒ⁶は芳香環を有しているかまたは有していない２価の有機基、ｑは０または１を示す。）
で表されるジオキセタン化合物が、入手の容易性、反応性、低吸湿性、得られる硬化物の力学的特性などの点から好ましく用いられる。

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

In the above general formula (VI), examples of R ⁵ include methyl, ethyl, propyl, butyl, and pentyl. Examples of R ⁶ include linear or branched alkylene groups having 1 to 12 carbon atoms (for example, ethylene group, propylene group, butylene group, neopentylene group, n-pentamethylene group, n-hexamethylene group, etc. ), A divalent group represented by the formula: —CH ₂ —Ph—CH ₂ — or —CH ₂ —Ph—Ph—CH ₂ —, hydrogenated bisphenol A residue, hydrogenated bisphenol F residue, hydrogenated A bisphenol Z residue, a cyclohexane dimethanol residue, a tricyclodecane dimethanol residue, etc. can be mentioned.

  Specific examples of the dioxetane compound represented by the general formula (VI) include the dioxetane compounds represented by the following formula (VIa) or (VIb).

（式中、２個のＲ⁵は互いに同じか又は異なる炭素数１〜５のアルキル基、Ｒ⁶は芳香環を有しているかまたは有していない２価の有機基を示す。）

(In the formula, two R ^{5 s} are the same or different from each other and have a C 1-5 alkyl group, and R ⁶ represents a divalent organic group having or not having an aromatic ring.)

  Specific examples of the dioxetane compound represented by the formula (VIa) include bis (3-methyl-3-oxetanylmethyl) ether, bis (3-ethyl-3-oxetanylmethyl) ether, bis (3-propyl- 3-oxetanylmethyl) ether, bis (3-butyl-3-oxetanylmethyl) ether, and the like.

Further, specific examples of the dioxetane compound represented by the above formula (VIb) include, in the above formula (VIb), two R ⁵ groups are both methyl, ethyl, propyl, butyl or pentyl group, and R ⁶ is ethylene. Group, propylene group, butylene group, neopentylene group, n-pentamethylene group, n-hexamethylene group, etc.), represented by the formula: —CH ₂ —Ph—CH ₂ — or —CH ₂ —Ph—Ph—CH ₂ —. And dioxetane compounds that are a divalent group, a hydrogenated bisphenol A residue, a hydrogenated bisphenol F residue, a hydrogenated bisphenol Z residue, a cyclohexanedimethanol residue, and a tricyclodecanedimethanol residue. .

Among them, as the polyoxetane compound in the above formula (VIa), are two R ⁵ are both methyl or ethyl bis (3-methyl-3-oxetanylmethyl) ether and / or bis (3- Ethyl-3-oxetanylmethyl) ether is preferably used from the viewpoints of easy availability, low hygroscopicity, mechanical properties of the cured product, etc., and particularly bis (3-ethyl-3-oxetanylmethyl) ether is more preferably used. It is done.

  The resin composition for optical modeling of the present invention is 200 parts by mass or less of the oxetane compound (e) with respect to 100 parts by mass of the epoxy compound (a) in the resin composition for optical modeling. It is preferable to contain in the ratio of 10-100 mass parts especially from points, such as the improvement of the toughness of the optical modeling thing obtained from the resin composition for optical modeling, the mechanical physical property of a modeling thing, and heat resistance.

As described above, as long as the content of the oxetane compound is 1 to 30% by mass as described above, the resin composition for optical modeling according to the present invention uses only one kind of oxetane compound or two or more kinds. Either an oxetane compound may be used.
The resin composition for optical modeling of the present invention comprises a monooxetane compound [particularly a monooxetane monoalcohol represented by the above general formula (V)] and a polyoxetane compound [particularly a dioxentane represented by the above general formula (VI). Compound] is contained at a mass ratio of 95: 5 to 5:95, in addition to the effect of improving the toughness of the optically modeled product by containing the oxetane compound (e), the resin for optical modeling When the moisture and moisture absorption rate of the composition is extremely low and the resin composition for photofabrication is stored for a long period of time in a high humidity state, the absorption of moisture and moisture decreases and the initial high photocuring sensitivity It is also possible to achieve an effect that can be maintained over a long period of time.

Moreover, the resin composition for optical three-dimensional model | molding of this invention can contain the polyalkylene ether type compound by the case, and when it contains the polyalkylene ether type compound, the impact resistance of the three-dimensional model | molding thing obtained. The physical properties such as are improved.
As the polyalkylene ether compound, in particular the following general formula (VII):

A—O— (R ⁷ —O—) _r — (R ⁸ —O—) _s —A ′ (VII)

[Wherein, R ⁷ and R ⁸ are different linear or branched alkylene groups having 2 to 5 carbon atoms, and A and A ′ are each independently a hydrogen atom, alkyl group, phenyl group, acetyl group or benzoyl group. And r and s each independently represent 0 or an integer of 1 or more (provided that both r and s are not 0 at the same time). ]
A polyalkylene ether compound represented by the formula is preferably used.

In the polyalkylene ether compound represented by the above general formula (VII) [hereinafter sometimes referred to as “polyalkylene ether compound (VII)”], both r and s are integers of 1 or more, and r and s Are 3 or more, oxyalkylene units (alkylene ether units): —R ⁷ —O— and oxyalkyne units (alkylene ether units): —R ⁸ —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 (VII), specific examples of R ⁷ and R ⁸ 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 ⁷ and R ⁸ 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 (VII), specific examples of A and A ′ include a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a phenyl group, an acetyl group, and a benzoyl group. Among them, it is preferable that at least one of A and A ′, in particular, both are hydrogen atoms. When at least one of A and A ′ is a hydrogen atom, when the resin composition for optical three-dimensional modeling containing the polyalkylene ether compound is cured by irradiation with active energy rays, the polyalkylene ether compound The hydroxyl groups at both ends react with an epoxy compound, a radical polymerization initiator, and the like, and the polyalkylene ether compound is bonded in the cured resin, and properties such as impact resistance are further improved.

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

Suitable examples of the polyalkylene ether compound (VII) include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyethylene oxide-polypropylene oxide block copolymer, random copolymer of ethylene oxide and propylene oxide, formula An oxytetramethylene unit (alkyl-substituted) having an alkyl substituent represented by: —CH ₂ CH ₂ CH (R ⁹ ) CH ₂ O— (wherein R ⁹ is a lower alkyl group, preferably a methyl or ethyl group). Represented by a polyether having a tetramethylene ether unit having a group), the oxytetramethylene unit and the formula: —CH ₂ CH ₂ CH (R ⁹ ) CH ₂ O— (wherein R ⁹ is a lower alkyl group). Oxytetramethylene unit having an alkyl substituent May be polyethers in which are bonded at random. 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 ⁹ ) CH ₂ O— (wherein R ⁹ is preferably a polyether in which tetramethylene ether units having an alkyl substituent represented by a lower alkyl group are randomly bonded. In such a 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 modeling of the present invention contains a polyalkylene ether compound, the content of the polyalkylene ether compound (VII) is based on the total mass of the resin composition for optical three-dimensional modeling. It is preferable that it is 1-30 mass%, and it is more preferable that it is 2-20 mass%. Moreover, you may contain the 2 or more types of polyalkylene ether type compound simultaneously in the range which does not exceed the said content.

  As long as the effects of the present invention are not impaired, the resin composition for optical modeling of the present invention, if necessary, colorants such as pigments and dyes, antifoaming agents, leveling agents, thickeners, flame retardants, and antioxidants An appropriate amount of one or two or more of an agent, a filler (crosslinked polymer particles, silica, glass powder, ceramic powder, metal powder, etc.), and a modifying resin may be contained.

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 verification 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, etc. . In particular, the resin composition for optical modeling according to the present invention is effective for producing a shape confirmation model or a function test model of a precise part or the like. More specifically, for example, it can be effectively used for applications such as precision parts, electrical / electronic parts, furniture, building structures, automotive parts, various containers, castings, models, mother dies, processing, etc. .

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the examples. In the following examples, “parts” means parts by mass.
Moreover, in the following examples, the measurement of the viscosity, the curing depth (Dp), the critical curing energy (Ec), and the work curing energy (E ₁₀ ) of the resin composition for optical modeling, and the optical modeling object obtained by optical modeling. Mechanical properties [tensile properties (tensile rupture strength, tensile rupture elongation, tensile modulus), yield strength, bending properties (bending strength, flexural modulus)], shrinkage rate, hardness after molding (surface hardness) The measurement or calculation of the elongation rate under the heat distortion temperature and humidity of 80% was performed as follows.

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

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

(3) Tensile properties of the optically shaped article (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.

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

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

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

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

(7) Hardness after molding (surface hardness):
Using the "ASKER D-type hardness meter" manufactured by Kobunshi Keiki Co., Ltd., using the stereolithography (dumbbell-shaped test piece conforming to JIS K-7113) produced in the following examples and comparative examples, In accordance with K-6253, the surface hardness of the test piece was measured over time by the durometer method [immediately after molding, 1 hour, 2 hours, 1 day (24 hours) and 4 days (96 hours)]. .

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

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

<< Production Example 1 >> [Production of aromatic sulfonium compound (II-1)]
(1) 300 ml of ether and 150 ml of water were put into a 1 liter three-necked flask, and 40.65 g of 4-phenylthiophenyldiphenylsulfonium chloride represented by the following formula (IIa-1) was dissolved therein. From the dropping funnel, 45.2 g of lithium perfluorophosphate represented by the following formula (IIb-1) dissolved in 150 ml of water was added dropwise with stirring. After completion of dropping, the mixture was stirred for 1 hour, and then separated into an ether layer and an aqueous layer, and the ether layer was recovered.

(2) The recovered ether layer was washed twice with water, dried over sodium sulfate, then the ether was removed, and the target aromatic sulfonium compound (II) represented by the following formula (II-1) was obtained. Obtained in quantitative yield.
The aromatic sulfonium compound (II) obtained in this manner was subjected to ¹⁹ F-NMR using an NMR apparatus (“JNM-A400” manufactured by JEOL Ltd.) with ¹⁹ F-NMR as an observation frequency of 357 MHz and with proton non-decoupled as a solvent for deuterated chloroform. As measured. The standard of the peak position was set to -76.5 ppm for the ¹⁹ F peak of trifluoroacetic acid.
As a result, peaks were observed at 40 ppm (3F), 70 ppm (12F), and 172 ppm (4F), and the aromatic sulfonium compound (II) having the following formula (II-1) [aromatic sulfonium compound (II-1) It was confirmed that The phosphorus atom was also confirmed by ³¹ P-NMR.

<< Production Example 2 >> [Production of aromatic sulfonium compound (II-2)]
(1) 4-phenylthiophenyldiphenylsulfonium chloride represented by the above formula (IIa-1) and lithium perfluorophosphate represented by the following formula (IIb-2) as used in Production Example 1 The same procedure as in Production Example 1 was used to quantitatively obtain the aromatic sulfonium compound (II) [aromatic sulfonium compound (II-2)] represented by the following formula (II-2). Got in.
The obtained aromatic sulfonium compound (II-2) was subjected to ¹⁹ F-NMR analysis in the same manner as in Production Example 1. As a result, 44 ppm (1F), 80 ppm (3F), 82 ppm (6F), 88 ppm (12F) , A peak was observed at 116 ppm (6F), and it was confirmed that this was an aromatic sulfonium compound (II) [aromatic sulfonium compound (II-2)] having the following formula (II-2). The phosphorus atom was also confirmed by ³¹ P-NMR.

Example 1
(1) 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate (“UVR-6105” manufactured by DOW, USA) 100 parts, hydrogenated bisphenol A diglycidyl ether 500 parts, 3-hydroxymethyl- 100 parts of 3-ethyloxetane, 100 parts of bis (3-ethyl-3-oxetanylmethyl) ether, 40 parts of the aromatic sulfonium compound (II-1) (cationic polymerization initiator) produced in Production Example 1 above, dipenta 200 parts of erythritol polyacrylate (“NK Ester A-9530” manufactured by Shin-Nakamura Chemical Co., Ltd.) and 20 parts of 1-hydroxy-cyclohexyl phenyl ketone (“Irgacure-184” manufactured by Ciba Specialty Chemicals, radical polymerization initiator) Mix well at room temperature (25 ° C) The stereolithography resin composition was prepared. It was 220 mPa * s (25 degreeC) when the viscosity of this resin composition for optical three-dimensional modeling was measured by the above-mentioned method.

(2) When the curing depth (Dp), critical curing energy (Ec), and work curing energy (E ₁₀ ) of the resin composition for optical modeling obtained in (1) above were measured by the methods described above, the following table was obtained. 1 as shown.
(3) A semiconductor laser (rated output: 1000 mW; wavelength: 355 nm) using an ultrahigh-speed stereolithography system (“SOLIFORM500B” manufactured by Nabtesco Corporation) using the resin composition for stereolithography obtained in (1) above; Spectra Physics "semiconductor-excited solid laser BL6 type", with a liquid level of 500 mW and a liquid level irradiation energy of 80 mJ / cm ² , a slice pitch (lamination thickness) of 0.10 mm and an average modeling time of 2 minutes per layer The optical three-dimensional modeling is performed to produce a dumbbell-shaped test piece according to JIS K-7113 for measuring physical properties, a bar-shaped test piece according to JIS K-7171, and a rectangular string-shaped shaped article. The physical properties were measured by the method described above, and the results are shown in Table 1 below.

<< Comparative Example 1 >>
As a photocationic initiator, an antimony-based photocationic initiator comprising a mixture of antimony-containing sulfonium salts represented by the following formulas (IIIa) and (IIIb) instead of the aromatic sulfonium compound (II-1) (US “UVI-6974” manufactured by DOW) was used, and the resin composition for optical modeling was manufactured in exactly the same manner as in Example 1, and optical modeling was performed in the same manner as in Example 1 using the resin composition. It was. The results are shown in Table 1 below.

Example 2
(1) The same 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate 200 parts used in Example 1, 400 parts hydrogenated bisphenol A diglycidyl ether (“Licar Resin HBE-100”) 200 parts of 3-hydroxymethyl-3-ethyloxetane, 40 parts of the aromatic sulfonium compound (II-1) (cationic polymerization initiator) produced in Production Example 1 above, dipentaerythritol polyacrylate (Shin Nakamura Chemical Co., Ltd.) 200 parts of “NK Ester A-9530” manufactured by the company and 20 parts of 1-hydroxy-cyclohexyl phenyl ketone (“Irgacure-184” manufactured by Ciba Specialty Chemicals, radical polymerization initiator) are good at room temperature (25 ° C.). By mixing, a resin composition for optical three-dimensional modeling was prepared. It was 185 mPa * s (25 degreeC) when the viscosity of this resin composition for optical three-dimensional modeling was measured by the above-mentioned method.

(2) When the curing depth (Dp), critical curing energy (Ec), and work curing energy (E ₁₀ ) of the resin composition for optical modeling obtained in (1) above were measured by the methods described above, the following table was obtained. 1 as shown.
(3) Using the resin composition for optical modeling obtained in (1) above, optical three-dimensional modeling is performed in the same manner as (4) of Example 1, and conforms to JIS K-7113 for measuring physical properties. A dumbbell-shaped test piece, a bar-shaped test piece according to JIS K-7171, and a rectangular string-shaped shaped article were prepared, and the physical properties thereof were measured by the method described above. The results are shown in Table 1 below.

<< Comparative Example 2 >>
As a photocation initiator, instead of the aromatic sulfonium compound (II-1), the same amount of the same antimony photocation initiator as used in Comparative Example 1 (“UVI-6974” manufactured by DOW, USA) was used. A resin composition for optical modeling was produced in exactly the same manner as in Example 2 except that it was used, and optical modeling was performed in the same manner as in Example 2 using it. The results are shown in Table 1 below.

Example 3
(1) 100 parts of the same 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate used in Example 1, 500 parts of hydrogenated bisphenol A diglycidyl ether (“Licaridine HBE-100”) 100 parts of 3-hydroxymethyl-3-ethyloxetane, 100 parts of Aronoxetane-121 (abbreviation: xylylene oxetane), aromatic sulfonium compound (II-2) produced in Production Example 2 above (cationic polymerization initiator) 40 parts, 200 parts of dipentaerythritol polyacrylate (“NK Ester A-9530” manufactured by Shin-Nakamura Chemical Co., Ltd.) and 1-hydroxy-cyclohexyl phenyl ketone (“Irgacure-184” manufactured by Ciba Specialty Chemicals), radical polymerization Initiator) 20 parts at room temperature By mixing well (25 ° C.), it was prepared for stereolithography resin composition. It was 330 mPa * s (25 degreeC) when the viscosity of this resin composition for optical three-dimensional modeling was measured by the above-mentioned method.

(2) When the curing depth (Dp), critical curing energy (Ec), and work curing energy (E ₁₀ ) of the resin composition for optical modeling obtained in (1) above were measured by the methods described above, the following table was obtained. 1 as shown.
(3) Using the resin composition for optical modeling obtained in (1) above, optical three-dimensional modeling is performed in the same manner as (4) of Example 1, and conforms to JIS K-7113 for measuring physical properties. A dumbbell-shaped test piece, a bar-shaped test piece according to JIS K-7171, and a rectangular string-shaped shaped article were prepared, and the physical properties thereof were measured by the method described above. The results are shown in Table 1 below.

<< Comparative Example 3 >>
As the photocation initiator, instead of the aromatic sulfonium compound (II-2), the same amount of the same antimony photocation initiator as used in Comparative Example 1 (“UVI-6974” manufactured by DOW, USA) was used. A resin composition for optical modeling was produced in exactly the same manner as in Example 2 except that it was used, and optical modeling was performed in the same manner as in Example 2 using it. The results are shown in Table 1 below.

<< Comparative Example 4 >>
(1) 550 parts of 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate (“UVR-6105” manufactured by DOW, USA), 50 parts of hydrogenated bisphenol A diglycidyl ether, 3-hydroxymethyl- 100 parts of 3-ethyloxetane, 100 parts of aronoxentane-121 (abbreviation: xylylene oxetane), 40 parts of aromatic sulfonium compound (II-2) (cationic polymerization initiator) produced in Production Example 2 above, dipenta 200 parts of erythritol polyacrylate (“NK Ester A-9530” manufactured by Shin-Nakamura Chemical Co., Ltd.) and 20 parts of 1-hydroxy-cyclohexyl phenyl ketone (“Irgacure-184” manufactured by Ciba Specialty Chemicals, radical polymerization initiator) Mix well at room temperature (25 ° C) There was prepared for stereolithography resin composition. It was 380 mPa * s (25 degreeC) when the viscosity of this resin composition for optical three-dimensional modeling was measured by the above-mentioned method.

(2) When the curing depth (Dp), critical curing energy (Ec), and work curing energy (E ₁₀ ) of the resin composition for optical modeling obtained in (1) above were measured by the methods described above, the following table was obtained. 1 as shown.
(3) Using the resin composition for optical modeling obtained in (1) above, optical three-dimensional modeling is performed in the same manner as (4) of Example 1, and conforms to JIS K-7113 for measuring physical properties. A dumbbell-shaped test piece, a bar-shaped test piece according to JIS K-7171, and a rectangular string-shaped shaped article were prepared, and the physical properties thereof were measured by the method described above. The results are shown in Table 1 below.

<< Comparative Example 5 >>
(1) 550 parts of 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate (“UVR-6105” manufactured by DOW, USA), 50 parts of hydrogenated bisphenol A diglycidyl ether, 3-hydroxymethyl- 100 parts of 3-ethyloxetane, 100 parts of Aronoxentane-121 (abbreviation: xylylene oxetane), 40 parts of the same antimony photocation initiator ("UVI-6974" manufactured by DOW, USA) used in Comparative Example 1 , 200 parts of dipentaerythritol polyacrylate (“NK Ester A-9530” manufactured by Shin-Nakamura Chemical Co., Ltd.) and 1-hydroxy-cyclohexyl phenyl ketone (“Irgacure-184” manufactured by Ciba Specialty Chemicals), radical polymerization initiator ) 20 parts at room temperature (2 ° C.) well mixed to prepare a stereolithography resin composition. It was 384 mPa * s (25 degreeC) when the viscosity of this resin composition for optical three-dimensional modeling was measured by the above-mentioned method.

(2) When the curing depth (Dp), critical curing energy (Ec), and work curing energy (E ₁₀ ) of the resin composition for optical modeling obtained in (1) above were measured by the methods described above, the following table was obtained. 1 as shown.
(3) Using the resin composition for optical modeling obtained in (1) above, optical three-dimensional modeling is performed in the same manner as (4) of Example 1, and conforms to JIS K-7113 for measuring physical properties. A dumbbell-shaped test piece, a bar-shaped test piece according to JIS K-7171, and a rectangular string-shaped shaped article were prepared, and the physical properties thereof were measured by the method described above. The results are shown in Table 1 below.

As is clear from the comparison between Example 1 and Comparative Example 1, the comparison between Example 2 and Comparative Example 2, and the comparison between Example 3 and Comparative Example 3, the epoxy compound is represented by the above general formula (I). Example 1 to 3 of the present invention using an alicyclic diglycidyl ether compound (I), an antimony-free aromatic sulfonium compound (II) as a photocationic initiator, and further containing an oxetane compound The resin composition for use has a high photocuring sensitivity equivalent to or surpassing that of the resin composition for optical modeling of Comparative Examples 1 to 3 using a conventional photocationic initiator containing antimony. And the optical modeling thing obtained using the resin composition for optical shaping | molding of this invention of Examples 1-3 is the physical property of Comparative Examples 1-3 using the conventional photocation initiator containing antimony. An optical modeling object obtained from the optical modeling resin composition of Comparative Examples 1 to 3, which is equivalent to or exceeds the optical modeling object obtained from the optical modeling resin composition Higher than that and excellent in toughness.
Moreover, the resin composition for optical shaping | molding of the comparative examples 4 and 5 is comparative example 4 and 5 by content of hydrogenated bisphenol A diglycidyl ether being less than 10 mass% with respect to the total mass of an epoxy compound. The optically shaped product obtained from the resin composition for optical modeling had a larger elongation rate than that of Examples 1 to 3 when left for 14 days under a humidity of 80%, and was inferior in dimensional stability over time.

<< Examples 4 to 7 >>
(1) The same 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate as used in Example 1, 100 parts of epoxy compound (in each example, the following epoxy compound is used) 500 parts, 50 parts of 3-hydroxymethyl-3-ethyloxetane, 150 parts of bis (3-ethyl-3-oxetanylmethyl) ether, aromatic sulfonium compound (II-2) produced in Production Example 2 (cationic polymerization initiator) ) 30 parts, 200 parts of dipentaerythritol polyacrylate (“NK Ester A-9530” manufactured by Shin-Nakamura Chemical Co., Ltd.) and 1-hydroxy-cyclohexyl phenyl ketone (“Irgacure-184” manufactured by Ciba Specialty Chemicals), radical 30 parts of (polymerization initiator) at room temperature (25 ° C.) Combined and were prepared for stereolithography resin composition.
[Type of epoxy compound used]
-Example 4: Hydrogenated bisphenol F diglycidyl ether-Example 5: Hydrogenated bisphenol Z diglycidyl ether-Example 6: Tricyclodecane dimethylol diglycidyl ether-Example 7: Licarresin DME-100
(2) When optical stereolithography was performed in the same manner as in (4) of Example 1 using each of the resin compositions for optical modeling obtained in (1) above, an aromatic sulfonium compound (II- The same amount of antimony photocationic initiator ("UVI-6974" manufactured by DOW, USA) is used in place of 2), and there is no inferiority in terms of curing performance compared to the case of stereolithography. In any of Examples 4 to 7, good photocuring was performed.

The resin composition for optical three-dimensional modeling of the present invention has high curing sensitivity by active energy rays, can produce the target three-dimensional modeled product with high productivity in a shortened modeling time, and is excellent in dimensional stability. It is possible to manufacture the desired optically shaped object with high modeling accuracy, and also has excellent toughness and durability, and excellent mechanical properties, water resistance, moisture resistance, heat resistance, etc. Because it contains a non-antimony aromatic sulfonium compound (II) that can form a model and is less toxic as a photocationic polymerization initiator, it is excellent in safety and handling, and contaminates the work environment and the global environment. Does not cause any deterioration.
Therefore, using the resin composition for optical three-dimensional modeling of the present invention, for precision parts, electrical / electronic parts, furniture, building structures, automotive parts, various containers, castings, molds, mother dies, etc. Modeling and processing models, parts for designing complex heat transfer circuits, parts for analyzing and planning the heat transfer behavior of complex structures, and other three-dimensional objects with complex shapes and structures at a high forming speed And it can be manufactured safely with dimensional accuracy.

Claims (3)

(I) Optical three-dimensional modeling resin containing an epoxy compound (a), a radical polymerizable organic compound (b), an active energy ray sensitive cationic polymerization initiator (c) and an active energy ray sensitive radical polymerization initiator (d) A composition;
(Ii) The epoxy compound (a) is represented by the following general formula (I);

(In the formula, ^Ra represents a hydrogenated bisphenol A residue, a hydrogenated bisphenol F residue, a hydrogenated bisphenol Z residue, a cyclohexanedimethanol residue, or a tricyclodecanedimethanol residue.)
An alicyclic diglycidyl ether compound represented by the formula (a) based on the total mass of the epoxy compound (a) in an amount of 30 to 100% by mass;
(Iii) The active energy ray-sensitive cationic polymerization initiator (c) is represented by the following general formula (II):

[In the above formula (I), R ¹ and R ² are each independently the following formulas (i) to (iv);

{In Formula (ii) and Formula (iv), X represents a chlorine atom or a fluorine atom}
R ³ is any one of the groups represented by the following formula (v);

Rf is a fluoroalkyl group having 1 to 8 carbon atoms, a is an integer of 0 to 3, b is an integer of 0 to 3, and c is 0 or 1, and a and b And c is 3, m is the same number as 1 + c, and n is an integer of 1 to 5. ]
An aromatic sulfonium compound represented by:
(Iv) The oxetane compound (e) is contained at a ratio of 5 to 200 parts by mass with respect to 100 parts by mass of the epoxy compound (a);
A resin composition for optical three-dimensional modeling characterized by the above.   The content ratio of epoxy compound (a): radical polymerizable organic compound (b) is 30:70 to 90:10 (mass ratio), and the aromatic sulfonium compound represented by the above general formula (II) is converted into an epoxy compound. It contains in the ratio of 0.1-10 mass% based on the mass of (a), and an active energy ray sensitive radical polymerization initiator (d) is 0.1-0.1 based on the mass of a radically polymerizable organic compound (b). The resin composition for optical three-dimensional model | molding of Claim 1 contained in the ratio of 20 mass%.   The method to manufacture an optical three-dimensional molded item using the resin composition for optical three-dimensional modeling of Claim 1 or 2.