WO2015080159A1 - Photo-curable composition for stereolithography, and method for producing 3d structure - Google Patents

Abstract

　Provided is a photo-curable composition for stereolithography with outstanding curing properties (reactivity), and with which it is possible to obtain a 3D structure having excellent heat resistance and mechanical properties through application to stereolithography.　The present invention pertains to a photo-curable composition for stereolithography, characterized by containing: an epoxy compound (a); a (meth)acrylic compound (b); and a photopolymerization initiator (c), wherein a compound containing an alicyclic epoxy group but not containing a carboxylic group within the molecule is contained as epoxy compound (a). The epoxy compound (a) is preferably at least one compound selected from the group consisting of: a compound having an alicyclic epoxy group within the molecule; an aromatic epoxy compound; and a compound having an alicyclic group and glycidyl ether within the molecule.

Description

Photo-curable composition for optical three-dimensional modeling, and method for manufacturing three-dimensional model

The present invention relates to a photocurable composition used in an optical three-dimensional modeling method, and a method for manufacturing a three-dimensional modeled product using the photocurable composition. This application claims the priority of Japanese Patent Application No. 2013-248240 for which it applied to Japan on November 29, 2013, and uses the content here.

In recent years, attention has been focused on an optical three-dimensional modeling method in which a three-dimensional model is produced by selectively irradiating light on a liquid photocurable composition based on three-dimensional CAD data. As a specific example of such an optical three-dimensional modeling method, for example, a cured product layer (resin having a desired shape pattern by selectively irradiating light onto a liquid surface of a photocurable composition filled in a container. Then, a photocurable composition for one layer is supplied onto the cured product layer, and similarly a cured product layer having a desired shape pattern is formed by light irradiation. A method of producing a three-dimensional object having a desired three-dimensional shape by repeating such a lamination operation (a lamination operation in which a new cured material layer is continuously formed on a previously formed cured material layer) is known. ing. In addition, the above-described cured product layer is formed by ejecting fine droplets of a photocurable composition from a nozzle by an inkjet method so as to draw a desired shape pattern, and curing this by light irradiation. An optical three-dimensional modeling method is also known. Such an optical three-dimensional modeling method does not require the use of a mold, and even if it has a complicated three-dimensional shape, it can be easily produced in a short time, which greatly increases the development period of various products. It is expected as a technology that contributes to rapid shortening and cost reduction.

As a photocurable composition (photocurable composition for optical three-dimensional modeling) used in the above-mentioned optical three-dimensional modeling method, for example, a monomer or oligomer that is liquid at 23 ° C. and can be polymerized by a ring-opening reaction, or A resin composition comprising a mixture of monomers and oligomers; an impact modifier comprising one or more block copolymers having at least one block composed of methyl methacrylate; and a curable composition comprising one or more polymerization initiators A thing is known (refer patent document 1).

Japanese translation of PCT publication 2010-520949

The photocurable composition used in the optical three-dimensional modeling method is required to have sufficient curability (reactivity) to form a cured product layer quickly by light irradiation. In addition, in recent years, three-dimensional objects obtained by optical three-dimensional modeling methods are not only used as models for various products and members, but are themselves used as molds and members, or as test parts for evaluation. Therefore, it is required to have excellent heat resistance and mechanical properties. However, the photocurable composition described in Patent Document 1 is insufficient from the viewpoint of satisfying all of such curability, heat resistance, and mechanical properties. In particular, the photocurable composition is inferior in curability, and has a problem that poor curing tends to occur during the optical three-dimensional modeling method.

Therefore, the object of the present invention is to provide a three-dimensional object that is excellent in curability (reactivity) and excellent in heat resistance and mechanical properties by being subjected to an optical three-dimensional modeling method. It is to provide a composition.

In recent years, in various fields, development of products that do not contain antimony is required in order to reduce adverse effects on the environment and the human body. For this reason, in the photocurable composition used for the optical three-dimensional modeling method, in addition to satisfying the above-described curability, heat resistance, and mechanical properties, it is possible to design a material that does not contain antimony. Is desired.

As a result of intensive studies to solve the above problems, the present inventor has obtained a photocurable composition containing an epoxy compound, a (meth) acrylic compound, and a photopolymerization initiator, and a specific epoxy compound as the epoxy compound. The present invention has been completed by finding that a three-dimensionally shaped article excellent in curability (reactivity) and excellent in heat resistance and mechanical properties can be formed by being subjected to an optical three-dimensional modeling method.

That is, the present invention includes (a) an epoxy compound, (b) a (meth) acrylic compound, and (c) a photopolymerization initiator, and (a) an epoxy compound having an alicyclic epoxy group in the molecule and a carbonyl Provided is a photocurable composition for optical three-dimensional modeling, comprising a compound having no group.

Furthermore, (a) the epoxy compound is at least one selected from the group consisting of a compound having an alicyclic epoxy group in the molecule, an aromatic epoxy compound, and a compound having an alicyclic ring and a glycidyl ether group in the molecule. The photocurable composition for optical three-dimensional modeling, which is a compound, is provided.

［式（Ｉ－１）中、Ｘ¹は、単結合、又はカルボニル基を有しない二価の基を示す。］
で表される化合物である前記の光学的立体造形用光硬化性組成物を提供する。 Further, a compound having an alicyclic epoxy group in the molecule and having no carbonyl group is represented by the following formula (I-1)

[In Formula (I-1), X ¹ represents a single bond or a divalent group having no carbonyl group. ]
The said photocurable composition for optical three-dimensional modeling which is a compound represented by these is provided.

Further, compounds having an alicyclic epoxy group in the molecule and no carbonyl group are 3,4,3 ′, 4′-diepoxybicyclohexyl, 2,2-bis (3,4-epoxycyclohexyl) propane, At least selected from the group consisting of 1,2-bis (3,4-epoxycyclohexyl) ethane, 2,3-bis (3,4-epoxycyclohexyl) oxirane, and bis (3,4-epoxycyclohexylmethyl) ether The photocurable composition for optical three-dimensional modeling which is one type of compound is provided.

Furthermore, the above-mentioned photocurable composition for optical three-dimensional modeling, which further comprises (a) an epoxy compound further containing a compound having an alicyclic epoxy group and a carbonyl group in the molecule.

［式（Ｉ－２）中、Ｘ²は、カルボニル基を有する二価の基を示す。］
で表される化合物である前記の光学的立体造形用光硬化性組成物を提供する。 Further, a compound having an alicyclic epoxy group and a carbonyl group in the molecule is represented by the following formula (I-2)

[In Formula (I-2), X ² represents a divalent group having a carbonyl group. ]
The said photocurable composition for optical three-dimensional modeling which is a compound represented by these is provided.

［式（ＩＩＩ）中、Ｒ^aは、水素原子又はメチル基を示す。Ｙは、単結合、炭素数１～１０のアルキレン基、又は、炭素数１～１０のアルキレン基の１以上とエーテル結合の１以上とが連結して形成された二価の基を示す。環Ｚは、環状脂肪族炭化水素基、又は脂環エポキシ基を示す。］
で表される化合物、及び多官能の脂肪族（メタ）アクリル化合物からなる群より選択される少なくとも一種の化合物を含む前記の光学的立体造形用光硬化性組成物を提供する。 Furthermore, as the (b) (meth) acrylic compound, the following formula (III)

[In the formula (III), R ^a represents a hydrogen atom or a methyl group. Y represents a single bond, an alkylene group having 1 to 10 carbon atoms, or a divalent group formed by linking one or more alkylene groups having 1 to 10 carbon atoms and one or more ether bonds. Ring Z represents a cyclic aliphatic hydrocarbon group or an alicyclic epoxy group. ]
And at least one compound selected from the group consisting of polyfunctional aliphatic (meth) acrylic compounds, and the above-mentioned photocurable composition for optical three-dimensional modeling.

Also, the present invention provides a method for producing a three-dimensional structure, characterized in that a three-dimensional structure is produced by an optical three-dimensional modeling method using the above-mentioned photocurable composition for optical three-dimensional modeling.

That is, the present invention relates to the following.

［式（Ｉ－１）中、Ｘ¹は、単結合、又はカルボニル基を有しない二価の基を示す。］
で表される化合物である［１］又は［２］に記載の光学的立体造形用光硬化性組成物。
　［４］式（Ｉ－１）におけるＸ¹が、単結合；炭素数１～６の直鎖又は分岐鎖状のアルキレン基；炭素数２～４のエポキシ化アルケニレン基、又は；炭素数１～４の直鎖又は分岐鎖状のアルキレン基の１以上とエーテル結合（－Ｏ－）の１以上とが連結して形成された総炭素数２～１０の二価の基である［３］に記載の光学的立体造形用光硬化性組成物。
　［５］（ｉ－１）分子内に脂環エポキシ基を有しカルボニル基を有しない化合物が、３，４，３'，４'－ジエポキシビシクロヘキシル、２，２－ビス（３，４－エポキシシクロヘキシル）プロパン、１，２－ビス（３，４－エポキシシクロヘキシル）エタン、２，３－ビス（３，４－エポキシシクロヘキシル）オキシラン、及びビス（３，４－エポキシシクロヘキシルメチル）エーテルからなる群より選択される少なくとも１種の化合物である［１］～［４］のいずれか１つに記載の光学的立体造形用光硬化性組成物。
　［６］（ａ）エポキシ化合物として、さらに、（ｉ－２）分子内に脂環エポキシ基及びカルボニル基を有する化合物を含む［１］～［５］のいずれか１つに記載の光学的立体造形用光硬化性組成物。
　［７］（ｉ－２）分子内に脂環エポキシ基及びカルボニル基を有する化合物が、下記式（Ｉ－２）

［式（Ｉ－２）中、Ｘ²は、カルボニル基を有する二価の基を示す。］
で表される化合物である［６］に記載の光学的立体造形用光硬化性組成物。
　［８］（ｉ－２）分子内に脂環エポキシ基及びカルボニル基を有する化合物が、後述の式（Ｉ－２－１）で表される化合物及び式（Ｉ－２－７）で表される化合物（特に、ｍが１である式（Ｉ－２－７）で表される化合物）からなる群より選択される少なくとも１種である［６］又は［７］に記載の光学的立体造形用光硬化性組成物。
　［９］（ａ）エポキシ化合物として、（ｉｉｉ）分子内に脂環及びグリシジルエーテル基を有する化合物を含む［１］～［８］のいずれか１つに記載の光学的立体造形用光硬化性組成物。
　［１０］（ａ）エポキシ化合物の含有量が、光硬化性組成物の全量（１００重量％）に対して、３０～９５重量％である［１］～［９］のいずれか１つに記載の光学的立体造形用光硬化性組成物。
　［１１］（ａ）エポキシ化合物の全量（１００重量％）に対する脂環式エポキシ化合物の割合が、６０～１００重量％である［２］～［１０］のいずれか１つに記載の光学的立体造形用光硬化性組成物。
　［１２］（ｉ）分子内に脂環エポキシ基を有する化合物と（ｉｉｉ）分子内に脂環及びグリシジルエーテル基を有する化合物の全量（１００重量％）に対する（ｉ）分子内に脂環エポキシ基を有する化合物の割合が、６０～９５重量％である［９］～［１１］のいずれか１つに記載の光学的立体造形用硬化性組成物。
　［１３］（ａ）エポキシ化合物の全量（１００重量％）に対する（ｉ－１）分子内に脂環エポキシ基を有しカルボニル基を有しない化合物の割合が、１～５０重量％である［１］～［１２］のいずれか１つに記載の光学的立体造形用硬化性組成物。
　［１４］（ｉ－１）分子内に脂環エポキシ基を有しカルボニル基を有しない化合物と（ｉ－２）分子内に脂環エポキシ基及びカルボニル基を有する化合物の全量（１００重量％）に対する（ｉ－１）分子内に脂環エポキシ基を有しカルボニル基を有しない化合物の割合が、５～５０重量％である［６］～［１３］のいずれか１つに記載の光学的立体造形用硬化性組成物。
　［１５］（ａ）エポキシ化合物以外のカチオン重合性化合物（その他のカチオン重合性化合物）を含む［１］～［１４］のいずれか１つに記載の光学的立体造形用硬化性組成物。
　［１６］その他のカチオン重合性化合物が、オキセタン化合物（特に、単官能オキセタン化合物）である［１５］に記載の光学的立体造形用硬化性組成物。
　［１７］その他のカチオン重合性化合物の含有量が、光硬化性組成物に含まれる（ａ）エポキシ化合物及びその他のカチオン重合性化合物の全量（１００重量％）に対して、１～４０重量％である［１５］又は［１６］に記載の光学的立体造形用硬化性組成物。
　［１８］オキセタン化合物（特に、単官能オキセタン化合物）の含有量が、（ａ）エポキシ化合物の全量１００重量部に対して、５～３０重量部である［１６］又は［１７］に記載の光学的立体造形用硬化性組成物。
　［１９］（ｂ）（メタ）アクリル化合物が分子内に有する（メタ）アクリロイル基の数（総数）が１～６個である［１］～［１８］のいずれか１つに記載の光学的立体造形用硬化性組成物。
　［２０］（ｂ）（メタ）アクリル化合物として、脂環式（メタ）アクリル化合物、芳香族（メタ）アクリル化合物、及び脂肪族（メタ）アクリル化合物からなる群より選択される少なくとも１種を含む［１］～［１９］のいずれか１つに記載の光学的立体造形用硬化性組成物。
　［２１］（ｂ）（メタ）アクリル化合物として、下記式（ＩＩＩ）

［式（ＩＩＩ）中、Ｒ^aは、水素原子又はメチル基を示す。Ｙは、単結合、炭素数１～１０のアルキレン基、又は、炭素数１～１０のアルキレン基の１以上とエーテル結合の１以上とが連結して形成された二価の基を示す。環Ｚは、環状脂肪族炭化水素基、又は脂環エポキシ基を示す。］
で表される化合物、及び多官能の脂肪族（メタ）アクリル化合物からなる群より選択される少なくとも一種の化合物を含む［１］～［２０］のいずれか１つに記載の光学的立体造形用光硬化性組成物。
　［２２］多官能の脂肪族（メタ）アクリル化合物が、３又は４官能の脂肪族（メタ）アクリル化合物である［２１］に記載の光学的立体造形用光硬化性組成物。
　［２３］（ｂ）（メタ）アクリル化合物の含有量が、（ａ）エポキシ化合物の全量１００重量部に対して、５～５０重量部である［１］～［２２］のいずれか１つに記載の光学的立体造形用光硬化性組成物。
　［２４］（ｂ）（メタ）アクリル化合物として、多環の脂環（特に橋架け炭素環）を有する単官能の（メタ）アクリル化合物（特に、Ｚが多環構造（特に、橋架け炭素環構造）を有する環状脂肪族炭化水素基である式（ＩＩＩ）で表される化合物）を含み、該化合物の割合が、（ｂ）（メタ）アクリル化合物の全量（１００重量％）に対して、１０～５０重量％である［２１］～［２３］のいずれか１つに記載の光学的立体造形用光硬化性組成物。
　［２５］（ｂ）（メタ）アクリル化合物として、脂環エポキシ基を有する単官能の（メタ）アクリル化合物（特に、Ｚが脂環エポキシ基である式（ＩＩＩ）で表される化合物）を含み、該化合物の割合が、（ｂ）（メタ）アクリル化合物の全量（１００重量％）に対して、１０～５０重量％である［２１］～［２４］のいずれか１つに記載の光学的立体造形用光硬化性組成物。
　［２６］（ｂ）（メタ）アクリル化合物として、多官能の脂肪族（メタ）アクリル化合物（特に、３又は４官能の脂肪族（メタ）アクリル化合物）を含み、該化合物の割合が、（ｂ）（メタ）アクリル化合物の全量（１００重量％）に対して、４０～８０重量％である［１］～［２５］のいずれか１つに記載の光学的立体造形用光硬化性組成物。
　［２７］（ｃ）光重合開始剤として、光カチオン重合開始剤及び光ラジカル重合開始剤のいずれか一方又は両方を含有する［１］～［２６］のいずれか１つに記載の光学的立体造形用光硬化性組成物。
　［２８］光カチオン重合開始剤が、非アンチモン系光カチオン重合開始剤である［２７］に記載の光学的立体造形用光硬化性組成物。
　［２９］光ラジカル重合開始剤が、非アンチモン系光ラジカル重合開始剤である［２７］又は［２８］に記載の光学的立体造形用光硬化性組成物。
　［３０］（ｃ）光重合開始剤の含有量が、光硬化性組成物に含まれる重合性化合物の全量１００重量部に対して、１～２０重量部である［１］～［２９］のいずれか１つに記載の光学的立体造形用光硬化性組成物。
　［３１］光カチオン重合開始剤の含有量が、光硬化性組成物に含まれる（ａ）エポキシ化合物及びその他のカチオン重合性化合物の全量１００重量部に対して、１～１５重量部である［２７］～［３０］のいずれか１つに記載の光学的立体造形用光硬化性組成物。
　［３２］光ラジカル重合開始剤の含有量が、光硬化性組成物に含まれる（ｂ）（メタ）アクリル化合物及びその他のラジカル重合性化合物の全量１００重量部に対して、１～３０重量部である［２７］～［３１］のいずれか１つに記載の光学的立体造形用光硬化性組成物。
　［３３］２５℃で液体である［１］～［３２］のいずれか１つに記載の光学的立体造形用光硬化性組成物。
　［３４］２５℃における粘度が０．１～１００００ｍＰａ・ｓである［１］～［３３］のいずれか１つに記載の光学的立体造形用光硬化性組成物。
　［３５］［１］～［３４］のいずれか１つに記載の光学的立体造形用光硬化性組成物を使用して光学的立体造形法により立体造形物を作製することを特徴とする立体造形物の製造方法。 [1] (a) an epoxy compound, (b) a (meth) acrylic compound, and (c) a photopolymerization initiator. (A) an epoxy compound having (i-1) an alicyclic epoxy group in the molecule A photocurable composition for optical three-dimensional modeling, comprising a compound having no carbonyl group.
[2] From the group consisting of (a) an epoxy compound comprising (i) a compound having an alicyclic epoxy group in the molecule, an aromatic epoxy compound, and (iii) a compound having an alicyclic ring and a glycidyl ether group in the molecule. The photocurable composition for optical three-dimensional modeling according to [1], which is at least one selected compound.
[3] (i-1) A compound having an alicyclic epoxy group in the molecule and having no carbonyl group is represented by the following formula (I-1):

[In Formula (I-1), X ¹ represents a single bond or a divalent group having no carbonyl group. ]
The photocurable composition for optical three-dimensional model | molding as described in [1] or [2] which is a compound represented by these.
[4] X ¹ in formula (I-1) is a single bond; a linear or branched alkylene group having 1 to 6 carbon atoms; an epoxidized alkenylene group having 2 to 4 carbon atoms; or [3], which is a divalent group having 2 to 10 total carbon atoms formed by linking one or more of 4 linear or branched alkylene groups and one or more of ether bonds (—O—) The photocurable composition for optical three-dimensional modeling of description.
[5] (i-1) A compound having an alicyclic epoxy group in the molecule and having no carbonyl group is 3,4,3 ′, 4′-diepoxybicyclohexyl, 2,2-bis (3,4 -Epoxycyclohexyl) propane, 1,2-bis (3,4-epoxycyclohexyl) ethane, 2,3-bis (3,4-epoxycyclohexyl) oxirane, and bis (3,4-epoxycyclohexylmethyl) ether The photocurable composition for optical three-dimensional modeling according to any one of [1] to [4], which is at least one compound selected from the group.
[6] The optical steric structure according to any one of [1] to [5], further comprising (a-2) an epoxy compound (i-2) a compound having an alicyclic epoxy group and a carbonyl group in the molecule. Photocurable composition for modeling.
[7] (i-2) A compound having an alicyclic epoxy group and a carbonyl group in the molecule is represented by the following formula (I-2):

[In Formula (I-2), X ² represents a divalent group having a carbonyl group. ]
The photocurable composition for optical three-dimensional model | molding as described in [6] which is a compound represented by these.
[8] (i-2) A compound having an alicyclic epoxy group and a carbonyl group in the molecule is represented by the following formula (I-2-1) and formula (I-2-7): [6] or [7], which is at least one selected from the group consisting of compounds (especially compounds represented by formula (I-2-7) wherein m is 1) Photocurable composition.
[9] The photo-curing property for optical three-dimensional modeling according to any one of [1] to [8], wherein (a) the epoxy compound includes (iii) a compound having an alicyclic ring and a glycidyl ether group in the molecule. Composition.
[10] The content of the epoxy compound (a) is 30 to 95% by weight with respect to the total amount (100% by weight) of the photocurable composition, as described in any one of [1] to [9] A photocurable composition for optical three-dimensional modeling.
[11] (a) The optical steric structure according to any one of [2] to [10], wherein the ratio of the alicyclic epoxy compound to the total amount (100% by weight) of the epoxy compound is 60 to 100% by weight. Photocurable composition for modeling.
[12] (i) alicyclic epoxy group in the molecule relative to the total amount (100% by weight) of (i) a compound having an alicyclic epoxy group in the molecule and (iii) a compound having an alicyclic ring and a glycidyl ether group in the molecule [9] The curable composition for optical three-dimensional modeling according to any one of [9] to [11], wherein the proportion of the compound having the above is 60 to 95% by weight.
[13] The ratio of the compound (i-1) having an alicyclic epoxy group in the molecule and not having a carbonyl group relative to the total amount (100% by weight) of the (a) epoxy compound is 1 to 50% by weight [1 ] The curable composition for optical three-dimensional modeling according to any one of [12] to [12].
[14] Total amount (100% by weight) of (i-1) a compound having an alicyclic epoxy group in the molecule and no carbonyl group and (i-2) a compound having an alicyclic epoxy group and a carbonyl group in the molecule (I-1) The optical component according to any one of [6] to [13], wherein the proportion of the compound having an alicyclic epoxy group in the molecule and having no carbonyl group is 5 to 50% by weight Three-dimensional modeling curable composition.
[15] The curable composition for optical three-dimensional modeling according to any one of [1] to [14], comprising (a) a cationically polymerizable compound other than an epoxy compound (other cationically polymerizable compounds).
[16] The curable composition for optical three-dimensional modeling according to [15], wherein the other cationically polymerizable compound is an oxetane compound (particularly a monofunctional oxetane compound).
[17] The content of the other cationic polymerizable compound is 1 to 40% by weight based on the total amount (100% by weight) of the epoxy compound and other cationic polymerizable compound contained in the photocurable composition. The curable composition for optical three-dimensional modeling according to [15] or [16].
[18] The optical system according to [16] or [17], wherein the content of the oxetane compound (particularly a monofunctional oxetane compound) is 5 to 30 parts by weight with respect to 100 parts by weight of the total amount of the (a) epoxy compound. Curable composition for three-dimensional modeling.
[19] The optical component according to any one of [1] to [18], wherein the number (total number) of (meth) acryloyl groups (b) in the molecule of the (b) (meth) acrylic compound is 1 to 6. Three-dimensional modeling curable composition.
[20] The (b) (meth) acrylic compound includes at least one selected from the group consisting of an alicyclic (meth) acrylic compound, an aromatic (meth) acrylic compound, and an aliphatic (meth) acrylic compound. [1] The curable composition for optical three-dimensional modeling according to any one of [19].
[21] (b) As the (meth) acrylic compound, the following formula (III)

[In the formula (III), R ^a represents a hydrogen atom or a methyl group. Y represents a single bond, an alkylene group having 1 to 10 carbon atoms, or a divalent group formed by linking one or more alkylene groups having 1 to 10 carbon atoms and one or more ether bonds. Ring Z represents a cyclic aliphatic hydrocarbon group or an alicyclic epoxy group. ]
And at least one compound selected from the group consisting of polyfunctional aliphatic (meth) acrylic compounds, and for optical three-dimensional modeling according to any one of [1] to [20] Photocurable composition.
[22] The photocurable composition for optical three-dimensional modeling according to [21], wherein the polyfunctional aliphatic (meth) acrylic compound is a trifunctional or tetrafunctional aliphatic (meth) acrylic compound.
[23] The content of the (b) (meth) acryl compound is 5 to 50 parts by weight with respect to 100 parts by weight of the total amount of the (a) epoxy compound, and any one of [1] to [22] The photocurable composition for optical three-dimensional modeling of description.
[24] (b) As a (meth) acrylic compound, a monofunctional (meth) acrylic compound having a polycyclic alicyclic ring (especially a bridged carbocyclic ring) (especially Z is a polycyclic structure (especially a bridged carbocyclic ring). A compound represented by formula (III) which is a cycloaliphatic hydrocarbon group having a structure), and the proportion of the compound is (b) relative to the total amount (100% by weight) of the (meth) acrylic compound, The photocurable composition for optical three-dimensional modeling according to any one of [21] to [23], which is 10 to 50% by weight.
[25] (b) As a (meth) acrylic compound, a monofunctional (meth) acrylic compound having an alicyclic epoxy group (particularly a compound represented by the formula (III) in which Z is an alicyclic epoxy group) The ratio of the compound is 10 to 50% by weight based on the total amount (100% by weight) of the (b) (meth) acrylic compound [21] to [24] A photocurable composition for three-dimensional modeling.
[26] (b) A polyfunctional aliphatic (meth) acrylic compound (particularly, a tri- or tetrafunctional aliphatic (meth) acrylic compound) is included as the (meth) acrylic compound, and the proportion of the compound is (b ) The photocurable composition for optical three-dimensional modeling according to any one of [1] to [25], which is 40 to 80% by weight relative to the total amount (100% by weight) of the (meth) acrylic compound.
[27] (c) The optical steric structure according to any one of [1] to [26], which contains one or both of a cationic photopolymerization initiator and a radical photopolymerization initiator as a photopolymerization initiator. Photocurable composition for modeling.
[28] The photocurable composition for optical three-dimensional modeling according to [27], wherein the cationic photopolymerization initiator is a non-antimony photocationic polymerization initiator.
[29] The photocurable composition for optical three-dimensional modeling according to [27] or [28], wherein the photoradical polymerization initiator is a non-antimony photoradical polymerization initiator.
[30] (c) The content of the photopolymerization initiator is 1 to 20 parts by weight with respect to 100 parts by weight of the total amount of the polymerizable compounds contained in the photocurable composition. The photocurable composition for optical three-dimensional model | molding as described in any one.
[31] The content of the photocationic polymerization initiator is 1 to 15 parts by weight with respect to 100 parts by weight of the total amount of the (a) epoxy compound and other cationically polymerizable compounds contained in the photocurable composition. [27] The photocurable composition for optical three-dimensional modeling according to any one of [30] to [30].
[32] The content of the photo radical polymerization initiator is 1 to 30 parts by weight with respect to 100 parts by weight of the total amount of (b) (meth) acrylic compound and other radical polymerizable compounds contained in the photocurable composition. The photocurable composition for optical three-dimensional modeling according to any one of [27] to [31].
[33] The photocurable composition for optical three-dimensional modeling according to any one of [1] to [32], which is liquid at 25 ° C.
[34] The photocurable composition for optical three-dimensional modeling according to any one of [1] to [33], which has a viscosity at 25 ° C. of 0.1 to 10,000 mPa · s.
[35] A three-dimensional object produced by an optical three-dimensional modeling method using the photocurable composition for optical three-dimensional modeling according to any one of [1] to [34] Manufacturing method of a model.

Since the photo-curable composition for optical three-dimensional modeling of the present invention has the above-described configuration, it is excellent in curability when irradiated with light. By subjecting the photo-curable composition to an optical three-dimensional modeling method, A three-dimensionally shaped object having a desired shape can be obtained. The said three-dimensional molded item is excellent in heat resistance and mechanical characteristics.

<Photocurable composition for optical three-dimensional modeling>
The photo-curable composition for optical three-dimensional modeling of the present invention (hereinafter sometimes simply referred to as “the photo-curable composition of the present invention”) includes (a) an epoxy compound, (b) a (meth) acrylic compound, And (c) a photocurable composition (photocurable resin composition) used for optical three-dimensional modeling, containing a photopolymerization initiator as an essential component. As described later, the photocurable composition of the present invention contains (a) a compound having an alicyclic epoxy group in the molecule and having no carbonyl group as an essential component as an epoxy compound.

In the present specification, (a) epoxy compound, (b) (meth) acryl compound, and (c) photopolymerization initiator are referred to as component (a), component (b), and component (c), respectively. There is a case. In the present specification, “(meth) acryl” means acryl and / or methacryl (any one or both of acryl and methacryl), and the same applies to “(meth) acryloyl” and the like.

[(A) Epoxy compound]
The (a) epoxy compound which is an essential component of the photocurable composition of the present invention is a compound having one or more epoxy groups (oxiranyl groups) in the molecule (in one molecule). However, the (a) epoxy compound does not include a compound corresponding to the (b) acrylic compound (that is, a compound having one or more epoxy groups and one or more (meth) acryloyl groups in the molecule). .

(A) As an epoxy compound, an alicyclic epoxy compound, an aromatic epoxy compound, an aliphatic epoxy compound etc. are mentioned, for example.

The alicyclic epoxy compound is a compound having one or more alicyclic rings (aliphatic hydrocarbon rings) and one or more epoxy groups in the molecule. The alicyclic epoxy compound may be a known or commonly used alicyclic epoxy compound, and is not particularly limited. For example, (i) two adjacent carbon atoms constituting the alicyclic ring in the molecule and A compound having an epoxy group composed of an oxygen atom (referred to as an “alicyclic epoxy group”); (ii) a compound in which an epoxy group is directly bonded to the alicyclic ring by a single bond; (iii) an alicyclic ring in the molecule And a compound having a glycidyl ether group (glycidyl ether type epoxy compound) and the like.

Examples of the alicyclic ring in the alicyclic epoxy compound include monocyclic alicyclic rings such as cyclopentane ring, cyclohexane ring, cyclooctane ring and cyclododecane ring (preferably 3 to 15 members, more preferably 5 or 6 members). A decaline ring (perhydronaphthalene ring), a perhydroindene ring (bicyclo [4.3.0] nonane ring), a perhydroanthracene ring, a perhydrofluorene ring, a perhydrophenanthrene ring, Norbornane ring (bicyclo [2.2.1] heptane ring), isobornane ring, adamantane ring, bicyclo [3.3.0] octane ring, tricyclo [5.2.1.0 ^2,6 ] decane ring, tricyclo [ 6.2.1.0 ^2,7 ] Polycyclic (about 2 to 4 rings) alicyclic ring (condensed carbocyclic ring, bridged carbocyclic ring, etc.) such as undecane ring. Moreover, the meaning of the alicyclic ring which comprises the above-mentioned alicyclic epoxy group is also contained in the alicyclic ring which the said alicyclic epoxy compound has in a molecule | numerator, for example.

The compound (i) having an alicyclic epoxy group in the molecule can be arbitrarily selected from known or commonly used compounds. (I) Examples of the alicyclic epoxy group in the compound having an alicyclic epoxy group in the molecule include an epoxycyclopentyl group, a 3,4-epoxycyclohexyl group, and 3,4-epoxytricyclo [5.2.1.0]. ^2,6 ] decane 8- (or 9) yl group (epoxidized dicyclopentadienyl group) and the like. Among them, the alicyclic epoxy group is preferably a 3,4-epoxycyclohexyl group from the viewpoint of heat resistance and mechanical strength of the three-dimensional structure. That is, (i) the compound having an alicyclic epoxy group in the molecule is preferably a compound having a 3,4-epoxycyclohexyl group.

The photocurable composition of the present invention is a compound having (i-1) an alicyclic epoxy group among (a) epoxy compounds from the viewpoints of curability, heat resistance of a three-dimensional structure, and mechanical properties, A compound having no carbonyl group in the molecule (that is, a compound having an alicyclic epoxy group and no carbonyl group in the molecule) is included as an essential component. The compound having an alicyclic epoxy group in the molecule and not having a carbonyl group is particularly a compound represented by the following formula (I-1) from the viewpoints of curability, heat resistance of a three-dimensional structure, and mechanical properties. Is particularly preferred.

In formula (I-1), X ¹ represents a single bond or a divalent group having no carbonyl group. Examples of the divalent group having no carbonyl group include, for example, a divalent hydrocarbon group, an alkenylene group in which a part or all of a carbon-carbon double bond is epoxidized, an ether bond, and a plurality of these linked. Groups and the like.

The compound in which X ¹ in the above formula (I-1) is a single bond includes 3,4,3 ′, 4′-diepoxybicyclohexyl (3,4,3 ′, 4′-diepoxybicyclohexane) Is mentioned.

Examples of the divalent hydrocarbon group include a linear or branched alkylene group having 1 to 18 carbon atoms, and a divalent alicyclic hydrocarbon group. Examples of the linear or branched alkylene group having 1 to 18 carbon atoms include a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group, and a trimethylene group. Examples of the divalent alicyclic hydrocarbon group include 1,2-cyclopentylene group, 1,3-cyclopentylene group, cyclopentylidene group, 1,2-cyclohexylene group, 1,3-cyclopentylene group, And divalent cycloalkylene groups (including cycloalkylidene groups) such as cyclohexylene group, 1,4-cyclohexylene group and cyclohexylidene group.

Examples of the alkenylene group in the alkenylene group in which part or all of the carbon-carbon double bond is epoxidized (sometimes referred to as “epoxidized alkenylene group”) include, for example, vinylene group, propenylene group, 1-butenylene group And straight-chain or branched alkenylene groups having 2 to 8 carbon atoms such as 2-butenylene group, butadienylene group, pentenylene group, hexenylene group, heptenylene group, octenylene group and the like. In particular, the epoxidized alkenylene group is preferably an alkenylene group in which all of the carbon-carbon double bonds are epoxidized, more preferably 2 to 4 carbon atoms in which all of the carbon-carbon double bonds are epoxidized. Alkenylene group.

As the compound (i-1) having an alicyclic epoxy group in the molecule and not having a carbonyl group, particularly from the viewpoint of curability of the photocurable composition, X ¹ is a single bond; A linear or branched alkylene group having ˜6; an epoxidized alkenylene group having 2 to 4 carbon atoms; or one or more linear or branched alkylene groups having 1 to 4 carbon atoms and an ether bond (—O A compound having a total number of 2 to 10 carbon atoms formed by linking one or more of-), more preferably 3,4,3 ', 4'-diepoxybicyclohexyl, 2, 2-bis (3,4-epoxycyclohexyl) propane, 1,2-bis (3,4-epoxycyclohexyl) ethane, 2,3-bis (3,4-epoxycyclohexyl) oxirane, bis (3,4-epoxy (Cyclohexylmethyl) ether is there.

The photocurable composition of the present invention includes (i-2) a compound having an alicyclic epoxy group as an alicyclic epoxy compound, and a compound having a carbonyl group in the molecule (that is, an alicyclic epoxy compound in the molecule). A compound having a group and a carbonyl group). In particular, from the viewpoint of balance between curability, heat resistance and mechanical properties of a three-dimensional structure, the photocurable composition of the present invention has (i-1) an alicyclic epoxy group in the molecule and a carbonyl group. It is preferable to include both a compound having no aliquot and a compound (i-2) having an alicyclic epoxy group and a carbonyl group in the molecule.

The compound (i-2) having an alicyclic epoxy group and a carbonyl group in the molecule is particularly represented by the following formula (I-2) from the viewpoint of the balance between the heat resistance and mechanical properties of the three-dimensional structure. Are preferred.

In formula (I-2), X ² represents a divalent group having a carbonyl group. Examples of the divalent group having a carbonyl group include a carbonyl group, an ester bond, an amide bond, a carbonate bond, a divalent group having a carbonyl group such as a group in which a plurality of these are linked; Examples thereof include a divalent group formed by linking one or more divalent groups and one or more divalent groups having no carbonyl group. Examples of the divalent group having no carbonyl group include X ^{1 in} the above formula (I-1) such as a divalent hydrocarbon group, an epoxidized alkenylene group, an ether bond, and a group in which a plurality of these are connected. And the groups exemplified as above.

Representative examples of the compound represented by the above formula (I-2) include compounds represented by the following formulas (I-2-1) to (I-2-10). In the following formulas (I-2-5) and (I-2-7), l and m each represents an integer of 1 to 30. R in the following formula (I-2-5) is an alkylene group having 1 to 8 carbon atoms, and includes a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, an isobutylene group, an s-butylene group, and a pentylene group. , A linear or branched alkylene group such as a hexylene group, a heptylene group, and an octylene group. Among these, linear or branched alkylene groups having 1 to 3 carbon atoms such as a methylene group, an ethylene group, a propylene group, and an isopropylene group are preferable. In the following formulas (I-2-9) and (I-2-10), n1 to n6 each represents an integer of 1 to 30.

The compound represented by the above formula (I-2) is particularly represented by the above formula (I-2-1) from the viewpoint of achieving both the heat resistance and mechanical properties of the three-dimensional structure at a higher level. A compound represented by the above formula (I-2-7) (particularly a compound represented by the formula (I-2-7) in which m is 1), more preferably a compound in which m is 1. It is a compound represented by (I-2-7).

Examples of the compound (ii) in which the epoxy group is directly bonded to the alicyclic ring with a single bond include compounds represented by the following formula (II).

In the formula (II), R ′ is a group (p-valent organic group) obtained by removing p hydroxyl groups (—OH) from the structural formula of p-valent alcohol, and p and n each represent a natural number. Examples of the p-valent alcohol [R ′ (OH) _p ] include polyhydric alcohols (such as alcohols having 1 to 15 carbon atoms) such as 2,2-bis (hydroxymethyl) -1-butanol. p is preferably 1 to 6, and n is preferably 1 to 30. When p is 2 or more, n in each group in () (inside the outer parenthesis) may be the same or different. Specific examples of the compound represented by the above formula (II) include 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol [for example, , Trade name “EHPE3150” (manufactured by Daicel Corporation), etc.].

Examples of the compound (iii) having an alicyclic ring and a glycidyl ether group in the molecule include glycidyl ethers of alicyclic alcohols (particularly, alicyclic polyhydric alcohols). More specifically, (iii) Examples of compounds having an alicyclic ring and a glycidyl ether group in the molecule include 2,2-bis [4- (2,3-epoxypropoxy) cyclohexyl] propane, 2,2- A compound obtained by hydrogenating a bisphenol A type epoxy compound such as bis [3,5-dimethyl-4- (2,3-epoxypropoxy) cyclohexyl] propane (hydrogenated bisphenol A type epoxy compound); bis [o, o -(2,3-epoxypropoxy) cyclohexyl] methane, bis [o, p- (2,3-epoxypropoxy) cyclohexyl] methane, bis [p, p- (2,3-epoxypropoxy) cyclo Hexyl] methane, bis [3,5-dimethyl-4- (2,3-epoxypropoxy) cyclohexyl] methane and other bisphenol F type epoxy Compound hydrogenated compound (hydrogenated bisphenol F type epoxy compound); Hydrogenated biphenol type epoxy compound; Hydrogenated phenol novolac type epoxy compound; Hydrogenated cresol novolak type epoxy compound; Hydrogenated cresol novolak type epoxy compound of bisphenol A; Examples thereof include hydrogenated naphthalene type epoxy compounds; hydrogenated epoxy compounds of epoxy compounds obtained from trisphenolmethane.

The aromatic epoxy compound is not particularly limited and may be a known or commonly used compound having one or more aromatic rings and one or more epoxy groups in the molecule. Examples of the aromatic ring that the aromatic epoxy compound has include a benzene ring, a biphenyl ring, a naphthalene ring, a fluorene ring, an anthracene ring, a stilbene ring, a dibenzothiophene ring, and a carbazole ring.

Specific examples of the aromatic epoxy compound include, for example, an epibis type glycidyl ether type epoxy obtained by a condensation reaction of bisphenols [for example, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, etc.] and epihalohydrin. Resins; high molecular weight epibis type glycidyl ether type epoxy resins obtained by further addition reaction of these epibis type glycidyl ether type epoxy resins with the above bisphenols; phenols [for example, phenol, cresol, xylenol, resorcin, catechol Bisphenol A, bisphenol F, bisphenol S, etc.] and aldehydes [eg formaldehyde, acetaldehyde, benzaldehyde, hydroxybenzal A novolac alkyl type glycidyl ether type epoxy resin obtained by condensation reaction of polyhydric alcohols obtained by condensation reaction with hydride, salicylaldehyde, etc.] with epihalohydrin; two phenol skeletons at the 9-position of the fluorene ring And an epoxy compound in which a glycidyl group is bonded to an oxygen atom in a state where a hydrogen atom is removed from a hydroxy group of the phenol skeleton, either directly or via an alkyleneoxy group.

The aliphatic epoxy compound is not particularly limited, and any known or commonly used epoxy compound having no cyclic structure such as an aromatic ring or an alicyclic ring in the molecule can be used. Examples of the aliphatic epoxy compound include a glycidyl ether of an alcohol having no q-valent cyclic structure (q is a natural number); a monovalent or polyvalent carboxylic acid [for example, acetic acid, propionic acid, butyric acid, stearic acid, Adipic acid, sebacic acid, maleic acid, itaconic acid, etc.] glycidyl ester; epoxidized oils and fats having double bonds such as epoxidized linseed oil, epoxidized soybean oil, epoxidized castor oil; polyolefins such as epoxidized polybutadiene (poly Epoxidized product of alkadiene). Examples of the alcohol having no q-valent cyclic structure include monohydric alcohols such as methanol, ethanol, 1-propyl alcohol, isopropyl alcohol and 1-butanol; ethylene glycol, 1,2-propanediol, 1 Divalent alcohols such as 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol; Examples include trihydric or higher polyhydric alcohols such as glycerin, diglycerin, erythritol, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, and sorbitol. That. The q-valent alcohol may be polyether polyol, polyester polyol, polycarbonate polyol, polyolefin polyol, or the like.

(A) As an epoxy compound, in particular, from the viewpoint of curability of a photocurable composition, heat resistance of a three-dimensional structure, and mechanical properties, (i) a compound having an alicyclic epoxy group in the molecule, an aromatic epoxy Compound, (iii) a compound having an alicyclic ring and a glycidyl ether group in the molecule is preferred, more preferably (i) a compound having an alicyclic epoxy group in the molecule, (iii) an alicyclic ring and a glycidyl ether group in the molecule It is a compound which has this. In particular, the photocurable composition of the present invention preferably contains both (i) a compound having an alicyclic epoxy group in the molecule and (iii) a compound having an alicyclic ring and a glycidyl ether group in the molecule. As described above, (i) a compound having an alicyclic epoxy group in the molecule includes (i-1) a compound having an alicyclic epoxy group in the molecule and having no carbonyl group, and (i-2) ) It is preferable to include both a compound having an alicyclic epoxy group and a carbonyl group in the molecule.

In the photocurable composition of the present invention, the (a) epoxy compound can be used alone or in combination of two or more. The (a) epoxy compound can be produced by a known or conventional method. Examples of the (a) epoxy compound include trade names “Celoxide 2021P”, “Epolide GT 401” (manufactured by Daicel Corporation); trade names “YX-8000” (manufactured by Mitsubishi Chemical Corporation), and the like. Commercial products can also be used.

The content (blending amount) of the epoxy compound (a) in the photocurable composition of the present invention is not particularly limited, but is 30 to 95% by weight with respect to the total amount (100% by weight) of the photocurable composition. More preferred is 40 to 90% by weight, still more preferred is 50 to 85% by weight. By setting the content to 30% by weight or more, there is a tendency that the dimensional accuracy, heat resistance, and mechanical properties of the three-dimensional structure are further improved. On the other hand, when the content is 95% by weight or less, the curability of the photocurable composition tends to be further improved.

The ratio of the alicyclic epoxy compound ((a) alicyclic epoxy compound which is an epoxy compound) to the total amount (100% by weight) of the (a) epoxy compound contained in the photocurable composition of the present invention is not particularly limited. However, it is preferably 60% by weight or more (for example, 60 to 100% by weight), more preferably 70 to 95% by weight, and still more preferably 80 to 90% by weight. There exists a tendency for the heat resistance of a three-dimensional molded item to improve more by making the said ratio into 60 weight% or more.

When the photocurable composition of the present invention includes (a) an epoxy compound that includes both (i) a compound having an alicyclic epoxy group in the molecule and (iii) a compound having an alicyclic ring and a glycidyl ether group in the molecule. , (I) having an alicyclic epoxy group in the molecule relative to the total amount (100% by weight) of the compound having an alicyclic epoxy group in the molecule and (iii) a compound having an alicyclic ring and a glycidyl ether group in the molecule The proportion of the compound is not particularly limited, but is preferably 60 to 95% by weight, more preferably 65 to 90% by weight, and still more preferably 70 to 90% by weight. There exists a tendency for the heat resistance of a three-dimensional molded item to improve more by making the said ratio into 60 weight% or more. On the other hand, when the ratio is 95% by weight or less, the mechanical properties of the three-dimensional modeled object tend to be further improved.

The ratio of the compound (i-1) having an alicyclic epoxy group in the molecule and not having a carbonyl group with respect to the total amount (100% by weight) of the (a) epoxy compound contained in the photocurable composition of the present invention is Although not limited, it is preferably 1 to 50% by weight, more preferably 5 to 40% by weight, and still more preferably 10 to 30% by weight. When the ratio is 1% by weight or more, the curability of the photocurable composition tends to be further improved. On the other hand, when the ratio is 50% by weight or less, the mechanical properties of the three-dimensional structure tend to be further improved.

The photocurable composition of the present invention includes (i) a compound having an alicyclic epoxy group in the molecule and (i-1) a compound having an alicyclic epoxy group in the molecule and no carbonyl group (i-2). ) When both a compound having an alicyclic epoxy group and a carbonyl group are included in the molecule, (i-1) a compound having an alicyclic epoxy group in the molecule and not having a carbonyl group and (i-2) The ratio of the compound (i-1) having an alicyclic epoxy group in the molecule and not having a carbonyl group with respect to the total amount (100% by weight) of the compound having an alicyclic epoxy group and a carbonyl group is not particularly limited. It is preferably 50% by weight, more preferably 8 to 40% by weight, still more preferably 10 to 30% by weight. There exists a tendency for the sclerosis | hardenability of a photocurable composition to improve more by making the said ratio into 5 weight% or more. On the other hand, when the ratio is 50% by weight or less, the curability of the photocurable composition and the mechanical properties of the three-dimensional structure tend to be improved in a balanced manner.

[Other cationic polymerizable compounds]
The photocurable composition of the present invention may contain (a) a cationically polymerizable compound other than the epoxy compound (sometimes referred to as “other cationically polymerizable compound”). Examples of other cationically polymerizable compounds include oxetane compounds (compounds having one or more oxetanyl groups in the molecule), vinyl ether compounds (compounds having one or more vinyl ether groups in the molecule), and the like.

Specific examples of the oxetane compound include 3,3-bis (vinyloxymethyl) oxetane, 3-ethyl-3- (hydroxymethyl) oxetane, and 3-ethyl-3- (2-ethylhexyloxymethyl). Oxetane, 3-ethyl-3-[(phenoxy) methyl] oxetane, 3-ethyl-3- (hexyloxymethyl) oxetane, 3-ethyl-3- (chloromethyl) oxetane, 3,3-bis (chloromethyl) Oxetane, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, bis {[1-ethyl (3-oxetanyl)] methyl} ether, 4,4′-bis [(3-ethyl- 3-Oxetanyl) methoxymethyl] bicyclohexyl, 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl ] Cyclohexane, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, 3-ethyl-3 {[(3-ethyloxetane-3-yl) methoxy] methyl)} oxetane, xyl Examples include lenbisoxetane, 3-ethyl-3-{[3- (triethoxysilyl) propoxy] methyl} oxetane, oxetanylsilsesquioxane, phenol novolac oxetane, and the like.

Specific examples of the vinyl ether compound include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxyisopropyl vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 2 -Hydroxybutyl vinyl ether, 3-hydroxyisobutyl vinyl ether, 2-hydroxyisobutyl vinyl ether, 1-methyl-3-hydroxypropyl vinyl ether, 1-methyl-2-hydroxypropyl vinyl ether, 1-hydroxymethylpropyl vinyl ether, 4-hydroxycyclohexyl vinyl ether, 1,6-hexanediol monovinyl ether, 1,6-hexanediol divinyl ether 1,4-cyclohexanedimethanol monovinyl ether, 1,4-cyclohexanedimethanol divinyl ether, 1,3-cyclohexanedimethanol monovinyl ether, 1,3-cyclohexanedimethanol divinyl ether, 1,2-cyclohexanedimethanol mono Vinyl ether, 1,2-cyclohexanedimethanol divinyl ether, p-xylene glycol monovinyl ether, p-xylene glycol divinyl ether, m-xylene glycol monovinyl ether, m-xylene glycol divinyl ether, o-xylene glycol monovinyl ether, o-xylene Glycol divinyl ether, diethylene glycol monovinyl ether, diethylene glycol divinyl ether, triethyleneglycol Monovinyl ether, triethylene glycol divinyl ether, tetraethylene glycol monovinyl ether, tetraethylene glycol divinyl ether, pentaethylene glycol monovinyl ether, pentaethylene glycol divinyl ether, oligoethylene glycol monovinyl ether, oligoethylene glycol divinyl ether, polyethylene glycol monovinyl ether, Polyethylene glycol divinyl ether, dipropylene glycol monovinyl ether, dipropylene glycol divinyl ether, tripropylene glycol monovinyl ether, tripropylene glycol divinyl ether, tetrapropylene glycol monovinyl ether, tetrapropylene glycol divinyl ether, penta Propylene glycol monovinyl ether, pentapropylene glycol divinyl ether, oligopropylene glycol monovinyl ether, oligopropylene glycol divinyl ether, polypropylene glycol monovinyl ether, polypropylene glycol divinyl ether, isosorbide divinyl ether, oxanorbornene divinyl ether, phenyl vinyl ether, n-butyl Examples thereof include vinyl ether, octyl vinyl ether, cyclohexyl vinyl ether, hydroquinone divinyl ether, 1,4-butanediol divinyl ether, and cyclohexane dimethanol divinyl ether.

Among these, as the other cationic polymerizable compound, an oxetane compound is preferable from the viewpoint of improving the curability of the photocurable composition and the toughness of the cured product, and more preferably an oxetane compound having one oxetane ring in the molecule ( Monofunctional oxetane compound).

In addition, in the photocurable composition of the present invention, the other cationic polymerizable compounds can be used alone or in combination of two or more. Other cationically polymerizable compounds can be produced by known or conventional methods. As other cationically polymerizable compounds, for example, commercially available products such as trade name “Aron Oxetane OXT-101” (manufactured by Toagosei Co., Ltd.) can be used.

The content (blending amount) of the other cationic polymerizable compound in the photocurable composition of the present invention is not particularly limited, but the (a) epoxy compound and other cationic polymerizable compounds contained in the photocurable composition are not limited. The amount is preferably 1 to 40% by weight, more preferably 5 to 30% by weight, based on the total amount (100% by weight). By setting the content of the other cationic polymerizable compound to 1% by weight or more, the curability of the photocurable composition tends to be further improved. On the other hand, when the content of the other cationic polymerizable compound is 40% by weight or less, the heat resistance of the three-dimensional structure tends to be further improved.

The content (blending amount) of the oxetane compound (particularly monofunctional oxetane compound) in the photocurable composition of the present invention is not particularly limited, but is 5 to 30 with respect to 100 parts by weight of the total amount of (a) epoxy compound. Part by weight is preferred, and more preferably 8 to 20 parts by weight. By setting the content of the oxetane compound (particularly, the monofunctional oxetane compound) to 5 parts by weight or more, the curability of the photocurable composition and the toughness of the cured product tend to be further improved. On the other hand, when the content of the oxetane compound (particularly, the monofunctional oxetane compound) is 30 parts by weight or less, the heat resistance of the three-dimensional structure tends to be further improved.

[(B) (Meth) acrylic compound]
The (b) (meth) acrylic compound in the photocurable composition of the present invention is a compound having one or more (meth) acryloyl groups in the molecule. (B) The number (total number) of (meth) acryloyl groups contained in the molecule of the (meth) acrylic compound is not particularly limited, but is preferably 1 to 6, more preferably 1 to 3. That is, the (b) (meth) acrylic compound may be a monofunctional (meth) acrylic compound having one (meth) acryloyl group in the molecule, or two or more (meth) acrylic compounds in the molecule. It may be a polyfunctional (meth) acryl compound having an acryloyl group.

(B) Examples of (meth) acrylic compounds include alicyclic (meth) acrylic compounds, aromatic (meth) acrylic compounds, and aliphatic (meth) acrylic compounds.

The alicyclic (meth) acrylic compound is a compound having one or more alicyclic rings (aliphatic hydrocarbon rings) and one or more (meth) acryloyl groups in the molecule. Examples of the alicyclic ring that the alicyclic (meth) acrylic compound has include monocyclic alicyclic rings such as cyclopentane ring, cyclohexane ring, cyclooctane ring, cyclododecane ring; decalin ring (perhydronaphthalene ring), Hydroindene ring (bicyclo [4.3.0] nonane ring), perhydroanthracene ring, perhydrofluorene ring, perhydrophenanthrene ring, perhydroacenaphthene ring, perhydrophenalene ring, norbornane ring (bicyclo [2. 2.1] heptane ring), isobornane ring, adamantane ring, bicyclo [3.3.0] octane ring, tricyclo [5.2.1.0 ^2,6 ] decane ring, tricyclo [6.2.1.0. ^2,7 ] Polycyclic alicyclic rings such as undecane rings (condensed carbocycles, bridged carbocycles, etc.) and the like. Moreover, the meaning of the alicyclic ring which comprises the above-mentioned alicyclic epoxy group is contained in the alicyclic ring which the said alicyclic (meth) acryl compound has in a molecule | numerator, for example. That is, the alicyclic (meth) acrylic compound includes a compound having a (meth) acryloyl group and an alicyclic epoxy group in the molecule.

Among them, from the viewpoint of heat resistance of the three-dimensional model, the alicyclic (meth) acrylic compound has a polycyclic alicyclic ring (particularly a bridged carbocyclic ring) and an alicyclic epoxy group as the alicyclic ring in the molecule. The constituting alicyclic ring is preferred. That is, as the alicyclic (meth) acrylic compound, a (meth) acrylic compound having a polycyclic alicyclic ring (particularly, a bridging carbocyclic ring) or a (meth) acrylic compound having an alicyclic epoxy group is preferable. A (meth) acrylic compound having an alicyclic epoxy group is preferred. Examples of the alicyclic epoxy group that the (meth) acrylic compound having an alicyclic epoxy group has include an epoxycyclopentyl ring, a 3,4-epoxycyclohexyl ring, and a 3,4-epoxytricyclo [ 5.2.1.0 ^2,6 ] decane 8- (or 9-) yl group and the like. Of these, a 3,4-epoxycyclohexyl ring and a 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane 8- (or 9-) yl group are preferable.

Examples of the alicyclic (meth) acrylic compound include compounds represented by the following formula (III) (monofunctional alicyclic (meth) acrylic compounds).

In the above formula (III), R ^a represents a hydrogen atom or a methyl group; Y represents a single bond, an alkylene group having 1 to 10 carbon atoms, or one or more alkylene groups having 1 to 10 carbon atoms and an ether bond ( A divalent group formed by linking one or more of —O—. Examples of the alkylene group having 1 to 10 carbon atoms include linear or branched alkylene having 1 to 10 carbon atoms such as a methylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, and a hexamethylene group. Groups and the like.

Y in the above formula (III) is particularly a single bond, an alkylene group having 1 to 6 carbon atoms, an alkyleneoxy group having 1 to 6 carbon atoms (the oxygen atom is at the right end), or an alkylene having 1 to 6 carbon atoms. A poly (alkyleneoxy) group (terminal oxygen atom at the right end) formed by bonding a plurality of oxy groups (for example, about 2 to 20) is preferred.

In the above formula (III), the ring Z represents a cyclic aliphatic hydrocarbon group or an alicyclic epoxy group. Examples of the cycloaliphatic hydrocarbon group include a cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, and a cyclododecyl group; a perhydronaphthalenyl group, a perhydroindenyl group (bicyclo [4.3. 0] nonyl group), perhydroanthracenyl group, perhydrofluorenyl group, perhydrophenanthrenyl group, perhydroacenaphthenyl group, perhydrophenanthrenyl group, norbornyl group (bicyclo [2. 2.1] heptyl group), isobornyl group, adamantyl group, bicyclo [3.3.0] octyl group, tricyclo [5.2.1.0 ^2,6 ] decyl group, tricyclo [6.2.1.0 ^2,7 ] and the like. Examples of the alicyclic epoxy group include epoxycyclopentyl ring, 3,4-epoxycyclohexyl ring, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane 8- (or 9-) yl. Groups and the like.

［上記式（ＩＩＩ－１）～（ＩＩＩ－３）中、Ｒ^a及びＹは、式（ＩＩＩ）におけるものと同じ。］ Specific examples of the compound represented by the above formula (III) include compounds represented by the following formulas (III-1) to (III-3).

[In the above formulas (III-1) to (III-3), R ^a and Y are the same as those in formula (III). ]

More specifically, examples of the alicyclic (meth) acrylic compound include cyclohexyl (meth) acrylate, cyclohexanemethanol (meth) acrylate, 1-adamantanol (meth) acrylate, and 1-adamantanmethanol (meth) acrylate. , Isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane methanol (meth) acrylate [= dicyclopentanyl (meth) acrylate], dicyclopentanyloxyethyl (meth) acrylate, etc. Monofunctional alicyclic (meth) acrylic compounds; 1,4-cyclohexanediol di (meth) acrylate, 1,4-cyclohexanedimethanol di (meth) acrylate, bicyclo [2.2.1] heptanedimethanol di ( (Meth) acrylate, 1,3-a Diamantane di (meth) acrylate, 1,3-adamantane dimethanol di (meth) acrylate, tricyclo [5.2.1.0 ^2,6] decanedimethanol di (meth) polyfunctional alicyclic acrylates such as (Meth) acrylic compound; 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-9-yl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, and the like.

Among them, the alicyclic (meth) acrylic compound is preferably a compound represented by the above formula (III), more preferably dicyclopentanyl (meth) acrylate, from the viewpoint of improving the heat resistance of the three-dimensional structure. 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane- 9-yl (meth) acrylate and 3,4-epoxycyclohexylmethyl (meth) acrylate, more preferably 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-8-yl ( (Meth) acrylate, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-9-yl (meth) acrylate.

The above aromatic (meth) acrylic compound is a compound having one or more aromatic rings and one or more (meth) acryloyl groups in the molecule. Examples of the aromatic ring that the aromatic (meth) acrylic compound has include a benzene ring, a biphenyl ring, a naphthalene ring, a fluorene ring, an anthracene ring, a stilbene ring, a dibenzothiophene ring, and a carbazole ring.

Specific examples of the aromatic (meth) acrylic compound include (meth) acrylic acid esters of bisphenols (for example, bisphenol A, bisphenol F, fluorene bisphenol, etc.); ethylene oxide and / or propylene of the bisphenols (Meth) acrylic acid ester of an adduct of oxide; two phenol skeletons are bonded to the 9-position of the fluorene ring, and oxygen atoms in the state in which a hydrogen atom is removed from the hydroxy groups of these two phenol skeletons are directly or (Meth) acrylic acid ester ((meth) acrylic acid ester having a bisarylfluorene skeleton) in which a (meth) acryloyl group is bonded via an alkyleneoxy group; a state in which a hydrogen atom is removed from two hydroxy groups of biphenol Oxygen field To, respectively, either directly or via a alkylene group (meth) acryloyl group is bonded (meth) acrylic acid ester.

The aliphatic (meth) acrylic compound may be a known or commonly used (meth) acrylic compound having no cyclic structure such as an aromatic ring or alicyclic ring in the molecule, and is not particularly limited. Examples of the aliphatic (meth) acrylic compound include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, and decyl (meth) acrylate. Monofunctional aliphatic (meth) acrylic compounds such as polyethylene glycol (meth) acrylate and polypropylene glycol (meth) acrylate; ethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6 -Hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) Of acrylate, glycerin di (or tri) (meth) acrylate, di (or tri) (meth) acrylate of glycerin ethylene oxide adduct, trimethylolpropane di (or tri) (meth) acrylate, ethylene oxide adduct of trimethylolpropane Di (or tri) (meth) acrylate, pentaerythritol di (or tri or tetra) (meth) acrylate, di (or tri or tetra) (meth) acrylate of pentaerythritol ethylene oxide adduct, dipentaerythritol di ( Or tri-, tetra-, penta-, or hexa) (meth) acrylate, di- or tri-, tetra-, tetra-, penta-, or hexa) (meth) acrylate polyfunctional fats such as dipentaerythritol ethylene oxide adduct (Meth) acrylic compounds.

As the (b) (meth) acrylic compound, in particular, from the viewpoint of the mechanical properties of the three-dimensional structure, a monofunctional (meth) acrylic compound or alicyclic ring having a polycyclic alicyclic ring (particularly a bridged carbocyclic ring). A monofunctional (meth) acrylic compound having an epoxy group and a polyfunctional aliphatic (meth) acrylic compound are preferable, more preferably a compound represented by the formula (III) and a polyfunctional aliphatic (meth) acrylic compound. is there. In particular, the photocurable composition of the present invention includes a compound represented by the formula (III) (one in which Z is a cyclic aliphatic hydrocarbon group or one in which Z is an alicyclic epoxy group) and a polyfunctional fat. It is preferable to include both a group (meth) acrylic compound (particularly a tri- or tetrafunctional aliphatic (meth) acrylic compound).

In the photocurable composition of the present invention, the (b) (meth) acrylic compound can be used alone or in combination of two or more. The (b) (meth) acrylic compound can be produced by a known or common method. Examples of (b) (meth) acrylic compounds include trade names “FA-129AS” and “FA-513AS” (manufactured by Hitachi Chemical Co., Ltd.); trade names “SR499” (manufactured by Sartomer). Commercially available products such as trade names “E-DCPA”, “Cyclomer” series (manufactured by Daicel Co., Ltd.) can also be used.

The content (blending amount) of (b) (meth) acrylic compound in the photocurable composition of the present invention is not particularly limited, but it is 5 to 50 parts by weight with respect to 100 parts by weight of the total amount of (a) epoxy compound. It is preferably 10 to 40 parts by weight, more preferably 15 to 30 parts by weight. (B) By making content of a (meth) acryl compound into 5 weight part or more, there exists a tendency which the sclerosis | hardenability of a photocurable composition improves more. On the other hand, when the content of the (b) (meth) acrylic compound is 50 parts by weight or less, the heat resistance of the three-dimensional structure tends to be further improved.

The photocurable composition of the present invention is a monofunctional (meth) acrylic compound (in particular, Z is a polycyclic structure) having a polycyclic alicyclic ring (especially a bridged carbon ring) as the (b) (meth) acrylic compound. (In particular, a compound represented by the formula (III) which is a cyclic aliphatic hydrocarbon group having a bridged carbocyclic structure), the proportion of the compound is the total amount of (b) (meth) acrylic compound ( 100 to 50% by weight), preferably 10 to 50% by weight, more preferably 20 to 40% by weight. There exists a tendency for the heat resistance of a three-dimensional molded item to improve more by making the said ratio into 10 weight% or more. On the other hand, when the ratio is 50% by weight or less, the mechanical properties of the three-dimensional structure tend to be further improved.

The photocurable composition of the present invention is a (b) (meth) acrylic compound having a monofunctional (meth) acrylic compound having an alicyclic epoxy group (particularly represented by the formula (III) wherein Z is an alicyclic epoxy group). The compound) is preferably 10 to 50% by weight, more preferably 20 to 40% by weight, based on the total amount of the (b) (meth) acrylic compound (100% by weight). is there. There exists a tendency for the heat resistance of a three-dimensional molded item to improve more by making the said ratio into 10 weight% or more. On the other hand, the mechanical strength of a three-dimensional molded item tends to be further improved by setting the ratio to 50% by weight or less.

When the photocurable composition of the present invention contains a polyfunctional aliphatic (meth) acrylic compound (particularly a tri- or tetrafunctional aliphatic (meth) acrylic compound) as the (b) (meth) acrylic compound, The proportion of the compound is preferably 40 to 80% by weight, more preferably 50 to 70% by weight, based on the total amount (100% by weight) of the (b) (meth) acrylic compound. There exists a tendency for the heat resistance of a three-dimensional molded item to improve more by making the said ratio into 40 weight% or more. On the other hand, the mechanical strength of a three-dimensional molded item tends to be further improved by setting the ratio to 80% by weight or less.

[Other radical polymerizable compounds]
The photocurable composition of the present invention may contain (b) a radical polymerizable compound other than the (meth) acrylic compound (sometimes referred to as “other radical polymerizable compound”). Other radical polymerizable compounds include, for example, styrene compounds [eg, styrene, α-methylstyrene, etc.], olefin compounds [eg, ethylene, propylene, isobutylene, butadiene, etc.], vinyl ester compounds [eg, acetic acid, etc. Known or commonly used radically polymerizable compounds such as vinyl etc. can be used.

In addition, in the photocurable composition of this invention, another radically polymerizable compound can also be used individually by 1 type, and can also be used in combination of 2 or more type. The photocurable composition of the present invention may not contain other radical polymerizable compounds. Other radically polymerizable compounds can be produced by known or conventional methods. In addition, a commercial item can also be used as another radically polymerizable compound.

The content (blending amount) of the other radical polymerizable compound in the photocurable composition of the present invention is not particularly limited, but the (a) (meth) acrylic compound and other radical polymerization contained in the photocurable composition are not particularly limited. It is preferably 10% by weight or less (for example, 0 to 5% by weight), more preferably 3% by weight or less, based on the total amount of the active compound (100% by weight). By setting the content of the other radical polymerizable compound to 10% by weight or less, there is a tendency that the heat resistance of the three-dimensional structure is further improved and defects such as coloring are suppressed.

[(C) Photopolymerization initiator]
The photopolymerization initiator (c) which is an essential component of the photocurable composition of the present invention is a polymerizable compound (cationic polymerizable) such as component (a) or component (b) in the photocurable composition by light irradiation. Compound, a radically polymerizable compound) that initiates or advances the polymerization reaction. (C) As a photoinitiator, well-known thru | or a usual photoinitiator can be used, Although it does not specifically limit, A photocationic polymerization initiator, a photoradical polymerization initiator, etc. are mentioned. Among these, from the viewpoint of more efficiently forming a cured product, the photocurable composition of the present invention may contain both a cationic photopolymerization initiator and a photoradical polymerization initiator as the photopolymerization initiator (c). preferable.

As the photocationic polymerization initiator, known or commonly used photocationic polymerization initiators can be used, and are not particularly limited. For example, sulfonium salt (salt of sulfonium ion and anion), iodonium salt (iodonium ion and Anion), selenium salt (selenium ion and anion salt), ammonium salt (ammonium ion and anion salt), phosphonium salt (phosphonium ion and anion salt), transition metal complex ion and anion Examples include salts.

Examples of the sulfonium salt include triphenylsulfonium salt, tri-p-tolylsulfonium salt, tri-o-tolylsulfonium salt, tris (4-methoxyphenyl) sulfonium salt, 1-naphthyldiphenylsulfonium salt, and 2-naphthyldiphenyl. Sulfonium salt, tris (4-fluorophenyl) sulfonium salt, tri-1-naphthylsulfonium salt, tri-2-naphthylsulfonium salt, tris (4-hydroxyphenyl) sulfonium salt, diphenyl [4- (phenylthio) phenyl] sulfonium salt , Triarylsulfonium salts such as 4- (p-tolylthio) phenyldi- (p-phenyl) sulfonium salt; diphenylphenacylsulfonium salt, diphenyl-4-nitrophenacylsulfonium salt, diphenylbenzi Diarylsulfonium salts such as sulfonium salt and diphenylmethylsulfonium salt; monoarylsulfonium salts such as phenylmethylbenzylsulfonium salt, 4-hydroxyphenylmethylbenzylsulfonium salt and 4-methoxyphenylmethylbenzylsulfonium salt; dimethylphenacylsulfonium salt, phena And trialkylsulfonium salts such as siltetrahydrothiophenium salt and dimethylbenzylsulfonium salt.

As the diphenyl [4- (phenylthio) phenyl] sulfonium salt, a trade name “CPI-101A” (manufactured by San Apro Co., Ltd., diphenyl [4- (phenylthio) phenyl] sulfonium hexafluoroantimonate 50% propylene carbonate solution), Product name “CPI-100P” (manufactured by San Apro Co., Ltd., diphenyl [4- (phenylthio) phenyl] sulfonium hexafluorophosphate 50% propylene carbonate solution), product name “K1-S” (manufactured by San Apro Co., Ltd., non-manufactured) Commercial products such as antimony triarylsulfonium salts) may be used.

Examples of the iodonium salt include diphenyliodonium salt, di-p-tolyliodonium salt, bis (4-dodecylphenyl) iodonium salt, bis (4-methoxyphenyl) iodonium salt, and the like.

Examples of the selenium salt include triaryl selenium such as triphenyl selenium salt, tri-p-tolyl selenium salt, tri-o-tolyl selenium salt, tris (4-methoxyphenyl) selenium salt, and 1-naphthyldiphenyl selenium salt. Salts; diaryl phenacyl selenium salts, diphenyl benzyl selenium salts, diaryl selenium salts such as diphenyl methyl selenium salts; monoaryl selenium salts such as phenyl methyl benzyl selenium salts; trialkyl selenium salts such as dimethyl phenacyl selenium salts .

Examples of the ammonium salt include tetramethylammonium salt, ethyltrimethylammonium salt, diethyldimethylammonium salt, triethylmethylammonium salt, tetraethylammonium salt, trimethyl-n-propylammonium salt, and trimethyl-n-butylammonium salt. Pyrodium salts such as alkylammonium salts; N, N-dimethylpyrrolidinium salts, N-ethyl-N-methylpyrrolidinium salts; N, N′-dimethylimidazolinium salts, N, N′-diethylimidazolinium salts, etc. Imidazolinium salts; tetrahydropyrimidinium salts such as N, N′-dimethyltetrahydropyrimidinium salt, N, N′-diethyltetrahydropyrimidinium salt; N, N-dimethylmorpholinium salt, N, N -Diethylmorpholinium Morpholinium salts such as salts; piperidinium salts such as N, N-dimethylpiperidinium salts and N, N-diethylpiperidinium salts; pyridinium salts such as N-methylpyridinium salts and N-ethylpyridinium salts; N, N ′ -Imidazolium salts such as dimethylimidazolium salt; Quinolium salts such as N-methylquinolium salt; Isoquinolium salts such as N-methylisoquinolium salt; Thiazonium salts such as benzylbenzothiazonium salt; And an acridium salt.

Examples of the phosphonium salt include tetraarylphosphonium salts such as tetraphenylphosphonium salt, tetra-p-tolylphosphonium salt, tetrakis (2-methoxyphenyl) phosphonium salt; triarylphosphonium salts such as triphenylbenzylphosphonium salt; Examples thereof include tetraalkylphosphonium salts such as benzylphosphonium salt, tributylbenzylphosphonium salt, tetraethylphosphonium salt, tetrabutylphosphonium salt, and triethylphenacylphosphonium salt.

Examples of the salt of the transition metal complex ion include chromium such as (η ⁵ -cyclopentadienyl) (η ⁶ -toluene) Cr ⁺ and (η ⁵ -cyclopentadienyl) (η ⁶ -xylene) Cr ^+. Salts of complex cations; salts of iron complex cations such as (η ⁵ -cyclopentadienyl) (η ⁶ -toluene) Fe ⁺ and (η ⁵ -cyclopentadienyl) (η ⁶ -xylene) Fe ⁺ It is done.

Examples of the anion (counter ion) for forming a salt with the cation include SbF ₆ ⁻ , PF ₆ ⁻ , BF ₄ ⁻ , (CF ₃ CF ₂ ) ₃ PF ₃ ⁻ , and (CF ₃ CF ₂ CF ₂ ). ₃ PF ₃ ⁻ , (C ₆ F ₅ ) ₄ B ⁻ , (C ₆ F ₅ ) ₄ Ga ⁻ , sulfonate anion (trifluoromethanesulfonate anion, pentafluoroethanesulfonate anion, nonafluorobutanesulfonate anion, methane Sulfonate anion, benzenesulfonate anion, p-toluenesulfonate anion), (CF ₃ SO ₂ ) ₃ C ⁻ , (CF ₃ SO ₂ ) ₂ N ⁻ , perhalogenate ion, halogenated sulfonate ion, sulfate ion , Carbonate ion, aluminate ion, hexafluorobismuth ion, carboxylate ion, arylborate ion, thiocyanate ion, nitrate ion Etc.

In the photocurable composition of the present invention, the photocationic polymerization initiator may be used alone or in combination of two or more. Examples of the cationic photopolymerization initiator include, for example, trade names “Syracure UVI-6970”, “Syracure UVI-6974”, “Syracure UVI-6990”, “Syracure UVI-950” (manufactured by Union Carbide, USA). ); Trade names “Irgacure 250”, “Irgacure 261”, “Irgacure 264”, “CG-24-61” (above, manufactured by BASF); trade names “SP-150”, “SP-151”, “SP” -170 "," Optomer SP-171 "(manufactured by ADEKA Corporation); trade name" DAICATII "(manufactured by Daicel Corporation); trade names" UVAC1590 "," UVAC1591 "(above, Daicel Cytec Corporation) Product name “CI-2064”, “CI-2039”, “CI-2624”, “C” -2481, "CI-2734", "CI-2855", "CI-2823", "CI-2758", "CIT-1682" (above, Nippon Soda Co., Ltd.); trade name "PI-2074" (Trade name “FFC509” (manufactured by 3M); trade names “BBI-102”, “BBI-101”, “BBI-103”, “MPI” -103 "," TPS-103 "," MDS-103 "," DTS-103 "," NAT-103 "," NDS-103 "(manufactured by Midori Chemical Co., Ltd.); trade name" CD-1010 " ”,“ CD-1011 ”,“ CD-1012 ”(above, manufactured by Sartomer, USA); trade names“ CPI-100P ”,“ CPI-101A ”(above, manufactured by San Apro Co., Ltd.) ) Etc. can also be used.

Among them, as the above-mentioned photocationic polymerization initiator, from the viewpoint of reducing adverse effects on the environment and the human body, a photocationic polymerization initiator not containing antimony as a constituent atom (non-antimony-based photocationic polymerization initiator; for example, SbF ₆ ⁻ Are preferred).

As the photo radical polymerization initiator, known or conventional photo radical polymerization initiators can be used, and are not particularly limited. For example, benzyl dimethyl ketone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl -1-phenylpropan-1-one, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2 -Methylpropan-1-one, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, acetophenone, dimethoxyacetophenone, dimethoxyphenylacetophenone, 2-methyl-1- [4- (methylthio) Phenyl] -2-morpholinopropane-1, ben In, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin phenyl ether, benzyldimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate (for example, methyl orthobenzoylbenzoate), 4- Ethyl dimethylaminobenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, tetra (t-butylperoxycarbonyl) benzophenone, 2,4-diethylthioxanthone, 2-amino-2-benzoyl-1-phenylalkane compound ( For example, 2-dimethylamino-2- (4-morpholino) benzoyl-1-phenylpropane and the like), aminobenzene derivatives (for example, 4,4- Sudiethylaminobenzophenone, etc.), imidazole compounds (eg, 2,2′-bis (2-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,2′-biimidazole, etc.), halomethylated triazines Compounds (for example, 2,6-bis (trichloromethyl) -4- (4-methoxynaphthalen-1-yl) -1,3,5-triazine, etc.), halomethyloxadiazole compounds (2-trichloromethyl-5 -(2-benzofuran-2-yl-ethenyl) -1,3,4-oxadiazole etc.), benzyl, diphenyl disulfite and the like.

In the photocurable composition of the present invention, the photocationic polymerization initiator can be used alone or in combination of two or more. Examples of the photocationic polymerization initiator include trade names “Kayacure EPA” and “Kayacure DETX” (manufactured by Nippon Kayaku Co., Ltd.); trade name “B-CIM” (Hodogaya Chemical Co., Ltd.). Commercially available products such as trade names “Irgacure 187” and “Irgacure 907” (manufactured by BASF) can also be used.

As the photo radical polymerization initiator, among them, a photo radical polymerization initiator not containing antimony as a constituent atom (non-antimony photo radical polymerization initiator) is preferable from the viewpoint of reducing adverse effects on the environment and the human body.

The content (blending amount) of the (c) photopolymerization initiator in the photocurable composition of the present invention is not particularly limited, but the total amount of the polymerizable compound contained in the photocurable composition [(a) epoxy compound, The total amount of other cationically polymerizable compounds, (b) (meth) acrylic compounds, and other radically polymerizable compounds] is preferably 1 to 20 parts by weight, more preferably 2 to 15 parts by weight with respect to 100 parts by weight. is there. (C) By making content of a photoinitiator into 1 weight part or more, there exists a tendency which can manufacture a three-dimensional molded item more efficiently by the optical three-dimensional modeling method. On the other hand, when the content of the (c) photopolymerization initiator is 20 parts by weight or less, the heat resistance and mechanical properties of the three-dimensional structure are further improved, and defects such as coloring tend to be suppressed.

Among them, the content (blending amount) of the photocationic polymerization initiator in the photocurable composition of the present invention is not particularly limited, but (a) an epoxy compound and other cationic polymerizable compounds contained in the photocurable composition The total amount is preferably 1 to 15 parts by weight, more preferably 2 to 10 parts by weight. By setting the content of the cationic photopolymerization initiator to 1 part by weight or more, there is a tendency that a three-dimensional model can be manufactured more efficiently by an optical three-dimensional model method. On the other hand, when the content of the cationic photopolymerization initiator is 15 parts by weight or less, the heat resistance and mechanical properties of the resulting three-dimensional structure are further improved, and defects such as coloring tend to be suppressed.

Further, the content (blending amount) of the photo radical polymerization initiator in the photo curable composition of the present invention is not particularly limited, but (b) (meth) acrylic compounds and other radicals contained in the photo curable composition. The amount is preferably 1 to 30 parts by weight, more preferably 2 to 20 parts by weight, based on 100 parts by weight of the total amount of the polymerizable compounds. By setting the content of the photoradical polymerization initiator to 1 part by weight or more, there is a tendency that a three-dimensional modeled object can be manufactured more efficiently by an optical three-dimensional model method. On the other hand, when the content of the radical photopolymerization initiator is 30 parts by weight or less, the heat resistance and mechanical properties of the resulting three-dimensional structure are further improved, and defects such as coloring tend to be suppressed.

[Photosensitizer]
The photocurable composition of the present invention may contain (c) a sensitizer (photosensitizer) for improving the sensitivity of the photopolymerization initiator. As the sensitizer, a known or conventional compound can be used as a sensitizer for a photopolymerization initiator, and is not particularly limited. For example, amine compounds (triethanolamine, methyldiethanolamine, triethylamine, diethylamine, etc.) ), Thioxanthone, thioxanthone derivatives (2-chlorothioxanthone, etc.), anthraquinone, anthraquinone derivatives, anthracene, anthracene derivatives, perylene, perylene derivatives, pyrene, pyrene derivatives, acridine, acridine derivatives (acridine orange, etc.), Examples include benzophenone, benzoin isopropyl ether, and benzoflavin. In addition, a sensitizer can also be used individually by 1 type, and can also be used in combination of 2 or more type. The content (blending amount) of the sensitizer is not particularly limited, and can be appropriately set according to the type and content of the (c) photopolymerization initiator to be used.

[Other ingredients]
The photocurable composition of the present invention may further contain a component other than the above-described components (may be referred to as “other components”) as necessary, as long as the effects of the present invention are not impaired. . Other components include, for example, dyes, pigments, impact imparting agents (for example, rubber particles, thermoplastic elastomers, etc.), fillers such as talc, curing expandable monomers, resins, adhesion improvers, reinforcing agents, softening agents Agent, plasticizer, viscosity modifier, thixotropic agent, solvent, inorganic or organic particles (such as nanoscale particles), antifoaming agent, leveling agent, coupling agent (such as silane coupling agent), surfactant Various stabilizers such as flame retardants, ultraviolet absorbers, antioxidants, anti-aging agents, light stabilizers, ion adsorbents, phosphors, mold release agents, pigment dispersants (for example, polymer dispersants), Conventional additives such as dispersion aids (for example, pigment derivatives and the like) and the like can be mentioned. The content (total amount) of other components in the photocurable composition of the present invention is not particularly limited, but is preferably less than 10 wt%, more preferably based on the total amount (100 wt%) of the photocurable composition. Less than 5% by weight.

The method for producing the photocurable composition of the present invention is not particularly limited, and a known or conventional method for producing a composition can be applied. The photocurable composition of the present invention can be prepared by, for example, stirring the above-described components while heating them as necessary and mixing them uniformly. In addition, the mixing | blending of each component in the case of the said stirring can also be implemented collectively, and can also be implemented sequentially. The stirring method is not particularly limited, and for example, known or conventional stirring means such as various mixers such as a dissolver and a homogenizer, a kneader, a roll, a bead mill, and a self-revolving stirrer can be used. Further, if necessary, after stirring and mixing, defoaming can be performed under vacuum.

The photocurable composition of the present invention preferably exhibits a liquid state (a liquid) at 25 ° C. Specifically, the viscosity at 25 ° C. of the photocurable composition of the present invention is not particularly limited, but is preferably 0.1 to 10000 mPa · s, more preferably 1 to 8000 mPa · s. By setting the viscosity at 25 ° C. to 0.1 mPa · s or more, the handleability of the photocurable composition tends to be further improved. On the other hand, by setting the viscosity at 25 ° C. to 10000 mPa · s or less, there is a tendency that it can be applied to a wider range of optical three-dimensional modeling methods, for example, it can be applied to an inkjet method because the viscosity is moderately low. The viscosity of the photocurable composition of the present invention at 25 ° C. is determined by using, for example, a digital viscometer (model number “DVU-EII type”, manufactured by Tokimec Co., Ltd.), rotor: standard 1 ° 34 ′ × R24. , Temperature: 25 ° C., rotation speed: 0.5 to 10 rpm.

<Method for manufacturing a three-dimensional model>
A three-dimensional model formed from a cured product of the photocurable composition can be produced (produced) by an optical three-dimensional modeling method using the photocurable composition of the present invention. The optical three-dimensional modeling method includes a well-known optical three-dimensional modeling method, and is not particularly limited. Specifically, for example, a desired shape pattern is formed on the photocurable composition (liquid) of the present invention. The cured product layer is formed by selectively irradiating light so that a cured product layer (cured product layer) is formed, and then the photocurable composition of the present invention for one layer on the cured product layer. In the same manner, a cured product layer having a desired shape pattern is formed by light irradiation, and a new cured product layer is continuously formed on such a laminating operation (a cured product layer formed in advance). A method for producing a three-dimensional structure having a desired three-dimensional shape by repeating a stacking operation to form; a microscopic droplet of the photocurable composition of the present invention is drawn from a nozzle by a inkjet method in a desired shape pattern Discharge to and irradiate light here Then, a cured product layer is formed, and then a single layer of the photocurable composition of the present invention is supplied onto the cured product layer by an ink jet method, and a cured product layer having a desired shape pattern is similarly formed by light irradiation. Further, by repeating such a laminating operation (a laminating operation in which a new cured product layer is continuously formed on the previously formed cured product layer), a three-dimensional modeled object having a desired three-dimensional shape is obtained. Examples of the method are as follows.

The light irradiated to cure the photocurable composition of the present invention in the optical three-dimensional modeling method is not particularly limited, and examples thereof include ultraviolet rays, visible rays, infrared rays, electron beams, X-rays, radiation, and high frequencies. It is done. Of these, ultraviolet rays are preferable in terms of handling and cost. As a light source in the case of using ultraviolet rays, for example, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a carbon arc, a metal halide lamp, sunlight, an LED lamp, a laser, or the like can be used.

In the optical three-dimensional modeling method, the method of selectively irradiating light to the photocurable composition of the present invention is not particularly limited, and for example, spotting is performed using light that has been focused in a spot shape such as laser light. Alternatively, known or commonly used selective light irradiation methods such as a method of irradiating light by a line drawing method and a method of irradiating light in a planar manner through a planar drawing mask can be used. Examples of the planar drawing mask include a mask formed by arranging a plurality of micro light shutters such as a liquid crystal shutter or a digital micromirror shutter (DMD).

In the manufacturing method of the three-dimensional modeled object of the present invention, after the three-dimensional modeled object is manufactured by the optical three-dimensional modeled method, the three-dimensional modeled object can be further subjected to post-curing treatment. Examples of the post-curing treatment method include known or conventional methods, and are not particularly limited. Examples thereof include a method of performing light irradiation, a method of performing heat treatment, a method of performing both light irradiation and heat treatment, and the like. It is done. The method of light irradiation or heat treatment is not particularly limited, and can be appropriately selected from known conditions. By performing such post-curing treatment, distortion and deformation generated in the three-dimensional structure can be reduced, and the appearance, heat resistance, mechanical properties, and the like of the three-dimensional structure may be improved. In addition, since the photocurable composition of this invention is excellent in sclerosis | hardenability and can fully advance hardening reaction by the light irradiation in an optical three-dimensional modeling method, it is not necessarily necessary to perform the above-mentioned post-curing process. .

Moreover, in the manufacturing method of the three-dimensional modeled object of the present invention, when the photocurable composition of the present invention remains on the surface of the three-dimensional modeled object obtained by the optical three-dimensional modeled method, it is necessary to remove it. It can also be washed according to The washing of the three-dimensional structure is not particularly limited, and for example, alcohols such as ethanol and isopropyl alcohol; ketones such as acetone and methyl ethyl ketone; esters such as ethyl acetate; and various organic solvents such as aliphatic hydrocarbons such as terpenes are used. Can be implemented. Moreover, the said three-dimensional molded item can also be wash | cleaned using a low-viscosity thermosetting resin and active energy ray curable resin (for example, photocurable composition of this invention etc.) instead of the said organic solvent. . In particular, when washing is performed using a thermosetting resin or an active energy ray curable resin, a curing treatment can be further performed after the washing.

The photocurable composition of the present invention can be widely used in the field of optical three-dimensional modeling, and is not particularly limited. For example, test parts (shape confirmation models and functions) such as various products and parts used in the products. Test model, etc.), master model for mold / mold production, and raw material for producing mold / mold, etc. The three-dimensional structure obtained by using the photocurable composition of the present invention can be used in various fields, and is not particularly limited. For example, the medical field (for example, artificial bones, artificial joints, human models, medical devices, and the like) As its members, etc.), it is used in the precision instrument field, electrical / electronic field, architectural field, automobile field, aircraft field, ship field, aerospace field, food field, daily life field, and the like.

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. In Table 1, “-” means that the component was not blended. The blending amounts of the trade names “CPI-100P” and “CPI-101A” in the following description and Table 1 are shown in terms of the amount of the product itself.

Example 1
[Production of photocurable composition]
As shown in Table 1, 3,4,3 ′, 4′-diepoxybicyclohexyl (Compound 1) 10 parts by weight, trade name “Celoxide 2021P” (manufactured by Daicel Corporation), 55 parts by weight, trade name “Aron” 10 parts by weight of Oxetane OXT-101 (manufactured by Toagosei Co., Ltd.), 10 parts by weight of trade name “YX-8000” (manufactured by Mitsubishi Chemical Corporation), trade name “FA-129AS” (Hitachi Chemical Industry Co., Ltd.) 5 parts by weight, product name “FA-513AS” (manufactured by Hitachi Chemical Co., Ltd.), 5 parts by weight “SR499” (manufactured by Sartomer), product name “CPI-100P” (San Apro ( 6 parts by weight) and 2 parts by weight of the product name “Irgacure 184” (manufactured by BASF), and a self-revolving stirrer (trade name “Awatori Nerita AR-250”, manufactured by Shinky Corp.) Use to mix evenly and degas Te photocurable composition (stereolithography photocurable composition) was prepared.

[Manufacture of 3D objects]
The manufacture of the three-dimensional model was performed by the optical three-dimensional model method (optical modeling).
Specifically, the photocurable composition obtained above is put in a resin tank, and the UV curable composition in the resin tank is cured by a UV lamp at a UV irradiation amount of 13.30 mJ / cm ² and a lamination pitch of 0.1 mm. By making it, the three-dimensional molded item (hardened | cured material) of length 100mm, width 100mm, and thickness 4mm was manufactured.

Examples 2 to 7, Comparative Examples 1 and 2
Except having changed the composition of the photocurable composition as shown in Table 1, it carried out similarly to Example 1, and manufactured the photocurable composition and the three-dimensional molded item.
In Comparative Examples 1 and 2, the photocurable composition could not be cured by the above-described production method, and a three-dimensional modeled object could not be obtained. For this reason, it was described in Table 1 as “hardening failure”.

The following evaluation was performed on the three-dimensional modeled object obtained above.

[Heat-resistant]
The three-dimensional model obtained above was processed into a size of 10 mm in length, 5 mm in width, and 4 mm in thickness to produce a test piece. The glass transition temperature (Tg, ° C.) of the test piece was measured using a thermomechanical measurement device (TMA) (manufactured by Seiko Instruments Inc.), and this was used as an index of heat resistance of the cured product. The results are shown in Table 1.

[Bending strength test (flexural modulus and bending strength)]
The three-dimensional model obtained above was processed into a size of 80 mm in length, 10 mm in width, and 4 mm in thickness to prepare a test piece. The bending strength test of the test piece was performed according to JIS K6911 under the condition of a bending speed of 1 mm / min, and the bending elastic modulus and bending strength were measured. The results are shown in Table 1.

As shown in Table 1, when the photocurable composition of the present invention was used (Examples), the photocurable composition was excellent in curability (reactivity), so that it was quickly obtained by an optical three-dimensional modeling method. A three-dimensional model was manufactured, and the three-dimensional model obtained was excellent in both heat resistance and mechanical properties. On the other hand, the curability of the photocurable compositions obtained in Comparative Examples 1 and 2 was insufficient, and it was impossible to produce a three-dimensional modeled object by the above-described optical three-dimensional modeling method. In addition, since the photocurable composition obtained in the Example is a non-antimony composition that does not contain antimony, it is less likely to adversely affect the environment and the human body. As shown in Comparative Examples 1 and 2, with the conventional composition, it was not possible to achieve both non-antimony material design and excellent curability.

The components used in Examples and Comparative Examples are as follows.
Compound 1: 3,4,3 ′, 4′-diepoxybicyclohexyl Compound 2: 2,2-bis (3,4-epoxycyclohexyl) propane Compound 3: 2,3-bis (3,4-epoxycyclohexyl) Oxirane Compound 4: Bis (3,4-epoxycyclohexylmethyl) ether Compound 5: 1,2-bis (3,4-epoxycyclohexyl) ethane Compound 6: Epoxidized dicyclopentenyl acrylate (E-DCPA)
CELLOXIDE 2021P: trade name “Celoxide 2021P” (manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate CELLOXIDE 2081: trade name “Celoxide 2081” (manufactured by Daicel Corporation) , Ε-caprolactone-modified 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate [compound represented by formula (I-2-7)]
OXT-101: Trade name “Aron Oxetane OXT-101” (manufactured by Toagosei Co., Ltd.), 3-ethyl-3- (hydroxymethyl) oxetane YX-8000: Trade name “YX-8000” (Mitsubishi Chemical Corporation) ), High-purity hydrogenated bisphenol A type epoxy resin FA-129AS: trade name “FA-129AS” (manufactured by Hitachi Chemical Co., Ltd.), nonanediol diacrylate FA-513AS: trade name “FA-513AS” (Hitachi) Kasei Kogyo Co., Ltd.), dicyclopentanyl acrylate SR499: trade name “SR499” (Sartomer), ethoxylated trimethylolpropane triacrylate CPI-100P: trade name “CPI-100P” (San Apro) ), PF ₆ triarylsulfonium salts solution in propylene carbonate CP -101A: (manufactured by San-Apro Ltd.) trade name "CPI-101A", SbF ₆ triarylsulfonium salts solution in propylene carbonate IRGACURE 184: trade name "Irgacure 184" (manufactured by BASF), a radical photopolymerization initiator

The photocurable composition of the present invention can be widely used in the field of optical three-dimensional modeling, for example, various products and parts used in the product, test parts (shape confirmation model, functional test model, etc.), It can be used as a raw material for producing a master model for mold / mold production, mold / mold, and the like.

Claims (8)

(A) an epoxy compound, (b) a (meth) acryl compound, and (c) a photopolymerization initiator, and (a) a compound having an alicyclic epoxy group in the molecule and no carbonyl group as the epoxy compound. A photocurable composition for optical three-dimensional modeling characterized by containing. (A) The epoxy compound is at least one compound selected from the group consisting of a compound having an alicyclic epoxy group in the molecule, an aromatic epoxy compound, and a compound having an alicyclic ring and a glycidyl ether group in the molecule. The photocurable composition for optical three-dimensional modeling according to claim 1. A compound having an alicyclic epoxy group in its molecule and no carbonyl group is represented by the following formula (I-1)

[In Formula (I-1), X ¹ represents a single bond or a divalent group having no carbonyl group. ]
The photocurable composition for optical three-dimensional model | molding of Claim 1 or 2 which is a compound represented by these. Compounds having an alicyclic epoxy group in the molecule and no carbonyl group are 3,4,3 ′, 4′-diepoxybicyclohexyl, 2,2-bis (3,4-epoxycyclohexyl) propane, 1, At least one selected from the group consisting of 2-bis (3,4-epoxycyclohexyl) ethane, 2,3-bis (3,4-epoxycyclohexyl) oxirane, and bis (3,4-epoxycyclohexylmethyl) ether The photocurable composition for optical three-dimensional modeling according to any one of claims 1 to 3, which is a compound of 5. The photocurable composition for optical three-dimensional modeling according to any one of claims 1 to 4, further comprising (a) a compound having an alicyclic epoxy group and a carbonyl group in the molecule as the epoxy compound. A compound having an alicyclic epoxy group and a carbonyl group in the molecule is represented by the following formula (I-2)

[In Formula (I-2), X ² represents a divalent group having a carbonyl group. ]
The photocurable composition for optical three-dimensional model | molding of Claim 5 which is a compound represented by these. (B) As the (meth) acrylic compound, the following formula (III)

[In the formula (III), R ^a represents a hydrogen atom or a methyl group. Y represents a single bond, an alkylene group having 1 to 10 carbon atoms, or a divalent group formed by linking one or more alkylene groups having 1 to 10 carbon atoms and one or more ether bonds. Ring Z represents a cyclic aliphatic hydrocarbon group or an alicyclic epoxy group. ]
The photo-curing for optical three-dimensional modeling according to any one of claims 1 to 6, comprising at least one compound selected from the group consisting of a compound represented by formula (II) and a polyfunctional aliphatic (meth) acrylic compound. Sex composition. A method for producing a three-dimensional structure, comprising producing a three-dimensional structure by an optical three-dimensional modeling method using the photocurable composition for optical three-dimensional modeling according to any one of claims 1 to 7. .