JP2017145301A - Photocurable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photocurable composition in which deterioration in optical molding properties due to addition of a light stabilizer is suppressed.SOLUTION: The photocurable composition contains a radically polymerizable monomer (A), a (bis)acylphosphine oxide-based photopolymerization initiator (B), a tertiary organophosphine compound (C), and a hindered amine compound (D). The hindered amine compound (D) is a light stabilizer having a structure represented by formula (I) (n is an integer of 4-12, and *and *each represent a bond).SELECTED DRAWING: None

Description

  The present invention relates to a photocurable composition, and more particularly to a photocurable composition suitable for optical three-dimensional modeling.

  In recent years, three-dimensional (3D) printers that model a three-dimensional object based on data representing the three-dimensional object have attracted attention and are being developed. In the case of performing optical three-dimensional modeling with a photofabrication type 3D printer, generally a photocurable composition containing a radical polymerizable monomer and a photopolymerization initiator is used. The photocurable composition used for the photo-forming type 3D printer is required to have characteristics not required for the conventional photocurable composition, such as high-precision moldability. For this reason, development of the photocurable composition suitable for optical fabrication type | mold 3D printer (namely, optical three-dimensional modeling use) is desired.

  On the other hand, Patent Document 1 discloses a photocurable resin composition used for optical three-dimensional modeling by a surface exposure method, to which the photocurable composition described in Patent Document 2 is applied. Specifically, Patent Document 1 discloses a photocurable resin composition used for optical three-dimensional modeling by a surface exposure method, which includes a photopolymerization initiator containing an acylphosphine oxide compound, a photopolymerizable monomer, and a third one. A photocurable resin composition containing a class organic phosphine compound is disclosed. Patent Document 1 describes that according to the photocurable resin composition, modeling accuracy can be improved.

JP2015-34245A Japanese Patent No. 4241956

  By the way, when producing a photocurable composition as a product, a light stabilizer is added from the viewpoint of storage stability. According to the study by the present inventors, it has been newly found that there is a problem that the optical formability is greatly impaired when an optical stabilizer is added to the photocurable composition and optical three-dimensional modeling is performed. It was.

  This invention is made | formed in view of this point, The objective is to provide the photocurable composition by which the fall of the optical modeling property by addition of a light stabilizer was suppressed.

  The photocurable composition of the present invention comprises a radical polymerizable monomer (A), a (bis) acylphosphine oxide photopolymerization initiator (B), a tertiary organic phosphine compound (C), and a hindered amine compound (D). contains. The hindered amine compound (D) includes a structure represented by the following formula (I).

(In the formula, n represents an integer of 4 to 12, and * ¹ and * ² each represent a bond.)

  In the present invention, the hindered amine compound (D) is preferably a compound represented by the following formula (II).

(In the formula, R ¹ represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and R ² represents a group represented by the following formula (III) or —COOR ⁴ (R ⁴ represents an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 4 to 12).

(In the formula, R ³ represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and * ³ represents a bond.)

  In the present invention, the tertiary organic phosphine compound (C) is preferably a compound represented by the following formula (IV).

(In the formula, R ^{5 to} R ⁷ each represents a phenyl group which may have a substituent.)

At this time, R ^{5 to} R ^{7 in the} formula (IV) are each preferably an m-methylphenyl group, a p-methylphenyl group, an m-methoxyphenyl group, or a p-methoxyphenyl group.

  In a preferred embodiment of the present invention, the hindered amine compound (D) is a compound represented by the following formula (II), wherein n of the formula (II) is an integer of 6 to 10, The tertiary organic phosphine compound (C) is tris (p-tolyl) phosphine or tris (p-anisyl) phosphine.

  In a more preferred embodiment of the present invention, the hindered amine compound (D) is a compound represented by the following formula (II), and n in the formula (II) is an integer of 7 to 9, The tertiary organic phosphine compound (C) is tris (p-tolyl) phosphine.

  The photocurable composition of the present invention is preferably for optical three-dimensional modeling.

  ADVANTAGE OF THE INVENTION According to this invention, the photocurable composition in which the fall of the optical shaping property by addition of a light stabilizer was suppressed is provided.

  The photocurable composition of the present invention comprises a radical polymerizable monomer (A), a (bis) acylphosphine oxide photopolymerization initiator (B), a tertiary organic phosphine compound (C), and a hindered amine compound (D). contains. The hindered amine compound (D) includes a structure represented by the following formula (I).

In formula (I), n represents an integer of 4 to 12, and * ¹ and * ² each represent a bond. Hereinafter, each component of the photocurable composition of the present invention will be described.

[Radically polymerizable monomer (A)]
The radically polymerizable monomer (A) is a component that cures the composition by photoradical polymerization. The radical polymerizable monomer (A) is a compound having at least one radical polymerizable group such as a vinyl group, a (meth) acryloyl group, and a styrene group. From the viewpoint of high photocurability, the radically polymerizable monomer (A) preferably has a (meth) acryloyl group. In particular, the radical polymerizable monomer (A) is preferably a (meth) acrylate compound. In the present specification, the description “(meth) acryloyl” means “methacryloyl” or “acryloyl”, and the description “(meth) acrylate” means “methacrylate” or “acrylate”. . A radically polymerizable monomer (A) can be used individually by 1 type or in combination of 2 or more type according to the characteristic of desired hardened | cured material.

  The radical polymerizable monomer (A) preferably contains a (meth) acrylate compound having two or more (meth) acryloyl groups, from the viewpoint of curability and mechanical properties of the cured product, and two (meth) acryloyl It is more preferable to include a (meth) acrylate compound having a group. The radical polymerizable monomer (A) preferably has an oxyethylene chain or an oxypropylene chain from the viewpoint of the mechanical properties of the cured product. Moreover, it is preferable that a radically polymerizable monomer (A) has a bisphenol skeleton from a viewpoint of the mechanical characteristic of hardened | cured material. A particularly preferred (meth) acrylate compound is a compound represented by the following formula (V) from the viewpoints of modeling accuracy, dimensional accuracy of a cured product, mechanical properties, and appearance.

In formula (V), R ⁸ and R ⁹ each represent an ethylene group or a propylene group (eg, 1,3-propylene group, 1,2-propylene group), and R ¹⁰ and R ¹¹ each represent a hydrogen atom. Or a methyl group, R ¹² and R ¹³ each represent a hydrogen atom or a methyl group, and m1 + m2 = 2 to 20. From the viewpoint of the mechanical properties of the cured product, each of R ⁸ and R ⁹ is preferably an ethylene group. Further, from the viewpoint of mechanical properties of the cured product, each of R ¹² and R ¹³ is preferably a methyl group. From the viewpoint of photocurability, each of R ¹⁰ and R ¹¹ is preferably a hydrogen atom. On the other hand, from the viewpoint of mechanical properties of the cured product, each of R ¹⁰ and R ¹¹ is preferably a methyl group.

The compound represented by the formula (V) can be synthesized according to a known method, and can also be obtained as a commercial product. Examples of commercially available products are “ABE-300 (R ⁸ and R ⁹ = ethylene group, R ¹⁰ and R ¹¹ = hydrogen atom, R ¹² and R ¹³ = methyl group, m1 + m2 = 3) manufactured by Shin-Nakamura Chemical Co., Ltd. ”,“ A-BPE-4 (R ⁸ and R ⁹ = ethylene group, R ¹⁰ and R ¹¹ = hydrogen atom, R ¹² and R ¹³ = methyl group, m1 + m2 = 4) ”,“ A-BPE-10 (R ⁸ and R ⁹ = ethylene group, R ¹⁰ and R ¹¹ = hydrogen atom, R ¹² and R ¹³ = methyl group, m1 + m2 = 10) ”,“ A-BPE-20 (R ⁸ and R ⁹ = ethylene group, R ¹⁰ And R ¹¹ = hydrogen atom, R ¹² and R ¹³ = methyl group, m1 + m2 = 17) ”,“ BPE-80N (R ⁸ and R ⁹ = ethylene group, R ¹⁰ and R ¹¹ = methyl group, R ¹² and And R ¹³ = methyl group, m1 + m2 = 2.3) ”,“ BPE-100 (R ⁸ and R ⁹ = ethylene group, R ¹⁰ and R ¹¹ = methyl group, R ¹² and R ¹³ = methyl group, m1 + m2 = 2) .6) ”,“ BPE-200 (R ⁸ and R ⁹ = ethylene group, R ¹⁰ and R ¹¹ = methyl group, R ¹² and R ¹³ = methyl group, m1 + m2 = 4) ”,“ BPE-500 (R ⁸ And R ⁹ = ethylene group, R ¹⁰ and R ¹¹ = methyl group, R ¹² and R ¹³ = methyl group, m1 + m2 = 10), “BPE-500 (R ⁸ and R ⁹ = ethylene group, R ¹⁰ and R ¹¹ = Methyl group, R ¹² and R ¹³ = methyl group, m1 + m2 = 17) ”;“ SR349 (R ⁸ and R ⁹ = ethylene group, R ¹⁰ and R ¹¹ ) manufactured by SARTOMER = Hydrogen atom, R ¹² and R ¹³ = methyl group, m1 + m2 = 3) ”,“ SR601 (R ⁸ and R ⁹ = ethylene group, R ¹⁰ and R ¹¹ = hydrogen atom, R ¹² and R ¹³ = methyl group, m1 + m2 = 4) "," SR602 ^{(R 8} and ^{R 9} = an ethylene ^{group, R 10} and ^{R 11} = hydrogen ^{atom, R 12} and ^{R 13} = methyl group, m1 + m @ 2 = 10) "," SR348 ^{(R 8} and ^R 9 = Ethylene group, R ¹⁰ and R ¹¹ = methyl group, R ¹² and R ¹³ = methyl group, m1 + m2 = 2) ”,“ SR480 (R ⁸ and R ⁹ = ethylene group, R ¹⁰ and R ¹¹ = methyl group, R ¹² And R ¹³ = methyl group, m1 + m2 = 10); “FA-321A manufactured by Hitachi Chemical Co., Ltd. (R ⁸ and R ⁹ = ethylene group, R ¹⁰ and R ¹¹ = water) Element, R ¹² and R ¹³ = methyl group, m1 + m2 = 10) ”,“ FA-324A (R ⁸ and R ⁹ = ethylene group, R ¹⁰ and R ¹¹ = hydrogen atom, R ¹² and R ¹³ = methyl group, m1 + m2 = 4) ”,“ FA-320M (R ⁸ and R ⁹ = ethylene group, R ¹⁰ and R ¹¹ = methyl group, R ¹² and R ¹³ = methyl group, m1 + m2 = 2) ”,“ FA-321M (R ⁸ and R ⁹ = ethylene group, R ¹⁰ and R ¹¹ = methyl group, R ¹² and R ¹³ = methyl group, m1 + m2 = 10) ”,“ FA-3218M (R ⁸ and R ⁹ = ethylene group, R ¹⁰ and R ¹¹ = methyl group, R ¹² and R ¹³ = methyl group, m1 + m2 = 18) ”;“ BPE-4 (R ⁸ and R ⁹ = ethylene group, R ¹⁰ And R ¹¹ = hydrogen atom, R ¹² and R ¹³ = methyl group, m1 + m2 = 4) ”,“ BPE-10 (R ⁸ and R ⁹ = ethylene group, R ¹⁰ and R ¹¹ = hydrogen atom, R ¹² and R ¹³ = Methyl group, m1 + m2 = 10) ”,“ BPE-20 (R ⁸ and R ⁹ = ethylene group, R ¹⁰ and R ¹¹ = hydrogen atom, R ¹² and R ¹³ = methyl group, m1 + m2 = 20) ”,“ BPP -4 (R ⁸ and R ⁹ = propylene group, R ¹⁰ and R ¹¹ = hydrogen atom, R ¹² and R ¹³ = methyl group, m1 + m2 = 4) ”,“ BPP-10 (R ⁸ and R ⁹ = propylene group, R ¹⁰ and R ¹¹ = hydrogen atom, R ¹² and R ¹³ = methyl group, m1 + m2 = 10) ”,“ BPP-20 (R ⁸ and R ⁹ = propylene group, R ¹⁰ and R ¹¹ = hydrogen atom, R ¹² and R ¹³ = methyl group, m1 + m2 = 20) ”;“ M-211B (R ⁸ and R ⁹ = ethylene group, R ¹⁰ and R ¹¹ = methyl group, R ¹² ) manufactured by Toagosei Co., Ltd. And R ¹³ = methyl group, m1 + m2 = 2) ”and the like.

  The radical polymerizable monomer (A) is a compound represented by the above formula (V), preferably 50% by mass or more, more preferably 70% by mass or more, based on the total weight of the radical polymerizable monomer (A). More preferably, it contains 80 mass% or more. The compounds represented by the above formula (V) can be used singly or in combination of two or more depending on the desired properties of the cured product.

  From the viewpoint of adjusting the viscosity of the composition and better mechanical properties of the cured product, the radical polymerizable monomer (A) is represented by the following formula (VI) in addition to the compound represented by the above formula (V). It is preferable that the compound further contains.

In the formula (VI), R ¹⁴ represents an ethylene group or a propylene group (eg, 1,3-propylene group, 1,2-propylene group), and R ¹⁵ and R ¹⁶ represent a hydrogen atom or a methyl group, respectively. M3 is 1-6, preferably 1-4.

The compound represented by the formula (VI) can be synthesized according to a known method, and can also be obtained as a commercial product. Examples of commercially available products are “A-200 (R ¹⁴ = ethylene group, R ¹⁵ and R ¹⁶ = hydrogen atom, m3 = 4)”, “1G (R ¹⁴ = ethylene group, R” manufactured by Shin-Nakamura Chemical Co., Ltd. ¹⁵ and R ¹⁶ = methyl group, m3 = 1) ”,“ 2G (R ¹⁴ = ethylene group, R ¹⁵ and R ¹⁶ = methyl group, m3 = 2) ”,“ 3G (R ¹⁴ = ethylene group, R ¹⁵ and R ¹⁶ = methyl group, m3 = 3) ”,“ 4G (R ¹⁴ = ethylene group, R ¹⁵ and R ¹⁶ = methyl group, m3 = 4) ”and the like.

  The radically polymerizable monomer (A) is preferably 1 to 30% by mass, more preferably 5 to 20% by mass of the compound represented by the formula (VI) with respect to the total mass of the radically polymerizable monomer (A). % Is included. The compounds represented by the above formula (VI) can be used singly or in combination of two or more depending on the desired properties of the cured product.

  The radical polymerizable monomer (A) may contain monofunctional (meth) acrylates such as methoxypolyethylene glycol (meth) acrylate, trifunctional or higher (meth) acrylates, and the like. Moreover, the radically polymerizable monomer (A) may contain urethane (meth) acrylate, ethoxylated isocyanuric acid tri (meth) acrylate and the like.

[(Bis) acylphosphine oxide photopolymerization initiator (B)]
The (bis) acylphosphine oxide photopolymerization initiator (B) is a component that initiates polymerization by generating radicals by light irradiation. The (bis) acylphosphine oxide-based photopolymerization initiator (B) is, for example, a known (bis) acylphosphine oxide compound used as a photopolymerization initiator for a photocurable composition, alone or Two or more types can be used in combination. The description “(bis) acylphosphine oxide” means “acylphosphine oxide” or “bisacylphosphine oxide”.

  Among the (bis) acylphosphine oxide photopolymerization initiator (B), examples of the acylphosphine oxide photopolymerization initiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and 2,6-dimethoxybenzoyldiphenylphosphine. Oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyldiphenyl Examples thereof include phosphine oxide and benzoyl di- (2,6-dimethylphenyl) phosphonate.

  Among the (bis) acylphosphine oxide photopolymerization initiator (B), examples of the bisacylphosphine oxide photopolymerization initiator include bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2, 6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, Bis- (2,6-dimethoxybenzoyl) phenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,5 -Dimethylphenylphosphine oxa , Bis - such as (2,4,6-trimethylbenzoyl) phenyl phosphine oxide.

  Examples of the (bis) acylphosphine oxide photopolymerization initiator (B) include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, and bis- (2,4,6 -Trimethylbenzoyl) phenylphosphine oxide is preferred.

  The (bis) acylphosphine oxide photopolymerization initiator (B) can be used alone or in combination of two or more. As content of (bis) acylphosphine oxide type photoinitiator (B), 0.1-10 mass parts is preferable with respect to 100 mass parts of radically polymerizable monomers (A), 0.5-5 mass parts Is more preferable.

[Tertiary organic phosphine compound (C)]
The tertiary organic phosphine compound (C) is a component that promotes radical polymerization. When the tertiary organic phosphine compound (C) is used in combination with the (bis) acylphosphine oxide photopolymerization initiator (B), it exhibits a particularly high radical polymerization promoting effect. As the tertiary organic phosphine compound (C), for example, known tertiary organic phosphine compounds used in the photocurable composition can be used singly or in combination of two or more. As the tertiary organic phosphine compound (C), for example, a compound represented by the following formula (IV) can be used.

In formula (IV), R ^{5 to} R ⁷ each represents an alkyl group, a cycloalkyl group, an aralkyl group, an alkenyl group, an alkynyl group, or an aryl group that may have a substituent.

R ^{5 to} R ⁷ are each preferably a phenyl group which may have a substituent. From the viewpoint of high formability, each of R ^{5 to} R ⁷ is more preferably a phenyl group having a substituent at the meta position or para position, and even more preferably a phenyl group having a substituent at the para position. . Examples of the substituent that the phenyl group may have include, for example, an alkyl group having 1 to 5 carbon atoms (eg, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, isobutyl group). , T-butyl group, pentyl group, etc.), C1-5 alkoxy group (eg, methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, t-butoxy group, pentyloxy group, etc.) A methyl group or a methoxy group is preferable. Therefore, particularly preferably as the tertiary organic phosphine compound (C), R ^{5 to} R ^{7 in} the above formula (IV) are each an m-methylphenyl group, a p-methylphenyl group, an m-methoxyphenyl group, or p. -A compound that is a methoxyphenyl group. That is, the tertiary organic phosphine compound (C) is particularly preferably tri (m-tolyl) phosphine, tri (p-tolyl) phosphine, tri (m-anisyl) phosphine, or tri (p-anisyl) phosphine. . When these compounds are used, particularly high formability is obtained. In addition, these compounds are higher in safety to the human body than compounds in which R ^{5 to} R ⁷ are phenyl groups (that is, triphenylphosphine). The tertiary organic phosphine compound (C) is most preferably tri (p-tolyl) phosphine or tri (p-anisyl) phosphine (particularly tri (p-tolyl) phosphine).

  The tertiary organic phosphine compound (C) can be used alone or in combination of two or more. As content of a tertiary organic phosphine compound (C), 0.01-5 mass parts is preferable with respect to 100 mass parts of radically polymerizable monomers (A), and 0.02-3 mass parts is more preferable.

[Hindered amine compound (D)]
The hindered amine compound (D) is a component that plays a role as a light stabilizer. In general, many light stabilizers trap radicals and thus inhibit the photocuring reaction. The degree of inhibition of this photocuring reaction is slight. However, when optical three-dimensional modeling is performed using a photocurable composition, even if the degree of inhibition of the photocuring reaction is slight, the modeling property is adversely affected. That is, when a light stabilizer is added to the photocurable composition, a decrease in accuracy in optical three-dimensional modeling, that is, a decrease in optical modeling property is observed. However, as a result of intensive studies by the present inventors, it has been found that by using a hindered amine compound having a specific structure among various light stabilizers, it is possible to suppress a decrease in formability due to the light stabilizer. The hindered amine compound (D) used in the present invention includes a structure represented by the following formula (I).

In formula (I), n represents an integer of 4 to 12, and * ¹ and * ² each represent a bond. Thus, the hindered amine compound (D) has a characteristic site in which the 2,2,6,6-tetramethylpiperidine structure and the linear alkylene structure are bonded through an ester bond. Although there is no restriction | limiting in particular about the structure couple | bonded with bond * ¹ and * ² , As a hindered amine compound (D) containing the structure represented by said Formula (I), the compound represented by following formula (II) is suitable. It is.

In the formula (II), R ¹ represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and R ² represents a group represented by the following formula (III) or —COOR ⁴ (R ⁴ represents an alkyl group having 1 to 4 carbon atoms), and n represents an integer of 4 to 12.

In formula (III), R ³ represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and * ³ represents a bond (bond bonded to the carbon atom to which R ² is bonded). Indicates.

The alkyl group having 1 to 10 carbon atoms represented by R ¹ and R ³ may be linear, branched or cyclic, and examples thereof include a methyl group, an ethyl group, and an n-propyl group. I-propyl group, n-butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, nonyl group, decyl group and the like. Especially, a C1-C8 linear alkyl group is preferable and a methyl group is more preferable.

The alkoxy group having 1 to 10 carbon atoms represented by R ¹ and R ³ may be linear, branched or cyclic, and examples thereof include methoxy, ethoxy, propoxy, iso Examples thereof include a propoxy group, an n-butoxy group, a t-butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a nonyloxy group, and a decyloxy group. Especially, a C1-C8 linear alkoxy group is preferable and n-octyloxy group is more preferable.

The alkyl group having 1 to 4 carbon atoms represented by R ⁴ may be either linear or branched, and examples thereof include a methyl group, an ethyl group, an n-propyl group, and an i-propyl group. , N-butyl group, isobutyl group, t-butyl group and the like. Of these, a methyl group is preferable.

  n is preferably an integer of 6 to 10, more preferably an integer of 7 to 9, and still more preferably 8.

A hindered amine compound (D) can be used individually by 1 type or in combination of 2 or more types. From the viewpoint of high shapability, hindered amine compound (D), preferably, in formula (II), R ¹ is a linear alkyl group having 1 to 8 carbon atoms or a straight alkoxy, R ² is a group represented by the above formula (III), n is an integer of 6 to 10, and R ³ is a straight chain having 1 to 8 carbon atoms in the formula (III). A compound having a linear alkyl group or a linear alkoxy group having 1 to 8 carbon atoms. The hindered amine compound (D) is more preferably a compound represented by the following formula (VII), or a mixture of a compound represented by the following formula (VIII) and a compound represented by the following formula (IX). More preferably, it is a mixture of a compound represented by the following formula (VIII) and a compound represented by the following formula (IX). The compound represented by the following formula (VII) can be obtained, for example, as Tinuvine 123 manufactured by BASF. A mixture of the compound represented by the following formula (VIII) and the compound represented by the following formula (IX) can be obtained, for example, as Tinuvine 292 manufactured by BASF.

  Moreover, according to the combination of a specific tertiary organic phosphine compound (C) and a specific hindered amine compound (D), the optical modeling property is particularly high. From the viewpoint of particularly high optical modeling, the hindered amine compound (D) represented by the above formula (II) and n is an integer of 6 to 10, and tris (p-tolyl) phosphine or tris (p-anisyl) phosphine. A combination of a hindered amine compound (D) represented by the above formula (II) and n being an integer of 7 to 9 and tris (p-tolyl) phosphine is more preferable.

  As content of a hindered amine compound (D), 0.01-5 mass parts is preferable with respect to 100 mass parts of radically polymerizable monomers (A), and 0.1-3 mass parts is more preferable.

  The photocurable composition of the present invention can be prepared by mixing each component according to a known method. The photocurable composition of the present invention basically has a liquid property.

  The photocurable composition of the present invention is, as necessary, a colorant such as a pigment or a dye, an antifoaming agent, a leveling agent, a thickener, a flame retardant, an oxidation, within a range that does not significantly impair the effects of the present invention. An additive such as an inhibitor and an ultraviolet absorber, a filler (crosslinked polymer particles, silica, glass powder, ceramic powder, metal powder, etc.) and the like may be contained.

  In the photocurable composition of the present invention, the reduction in the optical shaping property due to the addition of the light stabilizer is suppressed. Therefore, the photocurable composition of the present invention has good storage stability and stereolithography. Therefore, the photocurable composition of the present invention is suitable for optical three-dimensional modeling, and particularly suitable for optical three-dimensional modeling using a surface exposure method. That is, the photocurable composition of the present invention can be suitably used for optical three-dimensional modeling, and can be particularly suitably used for optical three-dimensional modeling by a surface exposure method. Moreover, the photocurable composition of the present invention includes, for example, a photocurable ink for an inkjet printer, a photocurable adhesive, a photocurable coating agent, a photocurable sealant, a photoresist material, and a photocurable molding material. Etc. can also be used.

  The three-dimensional model can be manufactured by a method including a step of curing the photocurable composition of the present invention with an optical three-dimensional model apparatus (particularly, a surface exposure type optical three-dimensional model apparatus). According to the manufacturing method, a highly accurate three-dimensional model can be obtained. A known optical structure type 3D printer or the like can be used for the optical three-dimensional modeling apparatus. As a specific example of the optical three-dimensional modeling of the surface exposure method, a photocured layer having a predetermined thickness is formed by irradiating ultraviolet light so that a desired pattern is obtained on the liquid surface of the photocurable composition of the present invention, Next, by supplying the photocurable composition of the present invention to this photocured layer, similarly irradiating with ultraviolet light, laminating the photocured layer continuous with the photocured layer, and repeating the lamination of the photocured layer A three-dimensional model can be obtained.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not restrict | limited to these Examples.

(Preparation of photocurable composition)
The components described in Table 1 were uniformly mixed at a mass ratio shown in Table 1 at about 60 ° C. to obtain photocurable compositions of Examples, Comparative Examples, and Reference Example 1. About the obtained photocurable composition, the optical shaping property was evaluated in the following procedure. The results are shown in Table 1.

[Optical modeling evaluation]
Using the photocurable composition of each Example, each Comparative Example and Reference Example 1, Roland Dee. Gee. An attempt was made to form quadrangular columns and cylinders of predetermined dimensions using a surface exposure 3D printer “ARM-10” (UV-LED light source) manufactured by the company. Regarding the modeling conditions, the stacking pitch was 0.15 mm, and the irradiation time was 25 seconds per layer. From the prototype results of the quadrangular column and cylinder, the formability was evaluated based on the following criteria.
Five points: A rectangular column of 1 mm × 1 mm and a cylinder of 1 mm in diameter could be formed.
4 points: A 1.5 mm × 1.5 mm square column and a cylinder with a diameter of 1.5 mm could be formed.
3 points: A square column of 2 mm × 2 mm and a cylinder of 2 mm in diameter could be formed.
2 points: A 2.5 mm × 2.5 mm square column and a 2.5 mm diameter cylinder could be formed.
1 point: A 3 mm × 3 mm square column and a 3 mm diameter cylinder could be formed.
0 point: A rectangular column and a cylinder could not be formed.

(Numerical values for each component in the table indicate mass percentages.)
A-BPE-10 (manufactured by Shin-Nakamura Chemical Co., Ltd.): ethoxylated bisphenol A diacrylate (in the formula (V), R ⁸ and R ⁹ are ethylene groups, R ¹⁰ and R ¹¹ are hydrogen atoms, R Compound in which ¹² and R ¹³ are methyl groups, and m1 + m2 = 10)
A-BPE-20 (manufactured by Shin-Nakamura Chemical Co., Ltd.): ethoxylated bisphenol A diacrylate (in the formula (V), R ⁸ and R ⁹ are ethylene groups, R ¹⁰ and R ¹¹ are hydrogen atoms, R Compound in which ¹² and R ¹³ are methyl groups and m1 + m2 = 17)
SR348 (manufactured by SARTOMER): ethoxylated bisphenol A dimethacrylate (in the formula (V), R ⁸ and R ⁹ are ethylene groups, R ¹⁰ and R ¹¹ are methyl groups, and R ¹² and R ¹³ are methyl groups) And m1 = 1 and m2 = 1)
1G (manufactured by Shin-Nakamura Chemical Co., Ltd.): ethylene glycol dimethacrylate 4G (manufactured by Shin-Nakamura Chemical Co., Ltd.): polyethylene glycol # 200 dimethacrylate FA-400M (manufactured by Hitachi Chemical Co., Ltd.): methoxypolyethylene glycol # 400 methacrylate Irgacure TPO (BASF 2,4,6-trimethylbenzoyldiphenylphosphine oxide TPTP (made by Hokuko Chemical Co., Ltd.): tri (p-tolyl) phosphine TMTP (made by Hokuko Chemical Co., Ltd.): tri (m-tolyl) phosphine TOTP (Hokuko) Chemical Industries): Tri (o-tolyl) phosphine Tinuvin 292 (BASF): Bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate (70-80%) and methyl 1, 2,2,6,6-pentamethyl-4-pi Rijirusebaketo mixtures (20-30%) (a mixture of the compound represented by the compound represented by formula (VIII) and the formula (IX))
Tinuvin 123 (manufactured by BASF): decanedioic acid bis (2,2,6,6-tetramethyl-1- (octyloxy) -4-piperidinyl) ester, reaction product of 1,1-dimethylethyl hydroperoxide and octane Product (compound represented by the above formula (VII))
Tinuvin 144 (BASF): bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl Malonate (compound represented by the following formula (X))
Tinuvin 5100 (manufactured by BASF): hindered amine compound LA-63P (manufactured by ADEKA): hindered amine compound (compound represented by the following formula (XI))

  Reference Example 1 is a photocurable composition that does not contain a hindered amine compound that is a light stabilizer and serves as a reference for stereolithography. In Comparative Example 1 in which Tinuvin 144 was used as the hindered amine compound, the optical modeling property was remarkably deteriorated, and a three-dimensional modeled object (square column and cylinder) could not be produced. In Comparative Example 2 in which Tinuvin 5100 was used as the hindered amine compound, the optical modeling performance was greatly reduced. In Comparative Example 3 in which LA-63P was used as the hindered amine compound, the optical modeling property was remarkably lowered, and a three-dimensional modeled object could not be produced. From these results, it can be seen that the addition of a light stabilizer (hindered amine compound) to the photocurable composition greatly affects the optical modeling. On the other hand, in Example 1 using Tinuvin 292 as the hindered amine compound, no reduction in stereolithography was observed. Moreover, in Example 2 using Tinuvin 123 as the hindered amine compound, there was a slight decrease in stereolithography. Tinuvin 292 and Tinuvin 123 have a common chemical structure represented by the above formula (I). Therefore, it can be seen from the above results that when a hindered amine compound containing a specific chemical structure is used as a light stabilizer, a decrease in the optical shaping property due to the addition of the light stabilizer is suppressed.

Further, in Examples 3 and 4 and Comparative Examples 4 and 5, the type of the tertiary organic phosphine compound was changed. R ⁵ to R ⁷ in the IV) is a phenyl group having a substituent at the para position compound> R ⁵ to R ⁷ in the formula (IV) is a phenyl group having a substituent at the meta position compound> the It turns out that it is the order of the compound whose R < ⁵ > -R < ⁷ > in Formula (IV) is a phenyl group which has a substituent in ortho position. In Examples 3 and 4, Tinuvin 292 was used as the hindered amine compound, and Tinuvin 5100 was used as the hindered amine compound in Comparative Examples 4 and 5. Here, the effect of the hindered amine compound on the optical shaping property was also observed. When Tinuvin 292 is changed to Tinuvin 5100 as the hindered amine compound, it can be seen that the optical shaping property is lowered.

  The photocurable composition of the present invention is suitable for optical three-dimensional modeling, and particularly suitable for optical three-dimensional modeling using a surface exposure method. Further, for example, it can also be used for photocurable inks for inkjet printers, photocurable adhesives, photocurable coating agents, photocurable sealants, photoresist materials, photocurable molding materials, and the like.

Claims (7)

Containing a radically polymerizable monomer (A), a (bis) acylphosphine oxide photopolymerization initiator (B), a tertiary organic phosphine compound (C), and a hindered amine compound (D);
The photocurable composition in which the said hindered amine compound (D) contains the structure represented by following formula (I).

(In the formula, n represents an integer of 4 to 12, and * ¹ and * ² each represent a bond.) The photocurable composition according to claim 1, wherein the hindered amine compound (D) is a compound represented by the following formula (II).

(In the formula, R ¹ represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and R ² represents a group represented by the following formula (III) or —COOR ⁴ (R ⁴ represents an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 4 to 12).

(In the formula, R ³ represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and * ³ represents a bond.) The photocurable composition according to claim 1 or 2, wherein the tertiary organic phosphine compound (C) is a compound represented by the following formula (IV).

(In the formula, R ^{5 to} R ⁷ each represents a phenyl group which may have a substituent.) The photopolymerizable property according to claim 3, wherein R ^{5 to} R ^{7 in the} formula (IV) are each an m-methylphenyl group, a p-methylphenyl group, an m-methoxyphenyl group, or a p-methoxyphenyl group. Composition.   The n in the formula (II) is an integer of 6 to 10, and the tertiary organic phosphine compound (C) is tris (p-tolyl) phosphine or tris (p-anisyl) phosphine. The photopolymerizable composition as described.   The photopolymerizable composition according to claim 2, wherein n in the formula (II) is an integer of 7 to 9, and the tertiary organic phosphine compound (C) is tris (p-tolyl) phosphine. The photocurable composition according to any one of claims 1 to 6, which is for optical three-dimensional modeling.