JP2014159556A - Photocurable composition for optical three-dimensional molding and method for manufacturing molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photocurable composition for optical three-dimensional molding, which can be easily cured by irradiation with a ray at a wavelength of 400 nm or more and which gives a molded article that can be easily detached from a container.SOLUTION: The photocurable composition for optical three-dimensional molding comprises: a radical polymerizable compound (A); a photopolymerization initiator (B) that generates a radical by irradiation with a ray at a wavelength of 400 nm or more; and a water-insoluble surfactant (C). A cured film having a film thickness of 30 μm obtained by irradiating the above photocurable composition with a ray at a wavelength of 400 nm or more has an elastic modulus of 10 to 500 MPa by a tension test; the cured film has a breaking strength of 1 to 50 MPa; and the cured film has a breaking elongation of 10 to 100%.

Description

  The present invention relates to a photocurable composition used when producing a three-dimensional structure by an optical three-dimensional modeling method, and a method for producing a three-dimensional object including a step of irradiating the photocurable composition with light having a wavelength of 400 nm or more. About.

  As a method for manufacturing a three-dimensional model, a method for manufacturing a three-dimensional model based on an optical three-dimensional modeling method such as an optical layered modeling method has been proposed. For example, each layer is formed from cross-sectional group data obtained by slicing 3D CAD data of a 3D model to be formed into a plurality of layers, and these layers are integrally laminated to produce a 3D model. An optical three-dimensional modeling method is known.

One aspect of this optical three-dimensional modeling method is carried out by repeating the following steps (1) and (2).
(1) A cured layer having a predetermined pattern is formed by selectively irradiating light such as a laser from above the support to the photocurable resin composition contained in the container.
(2) Lowering the support by one layer As described above, in the optical three-dimensional modeling method, a plurality of curings are performed by repeatedly forming a new cured layer integrally on the upper side of the previously formed cured layer. A three-dimensional structure in which layers are integrally formed can be manufactured.

  In recent years, studies have been made on reducing the size and weight of the apparatus for producing these three-dimensional objects and reducing the cost, and there is a demand for an inexpensive apparatus that can be used on a desktop and can be introduced into a general home. Optical stereolithography that is used in general households has a wide range of characteristics such as the molding is not easily scratched, the molding is flexible and safe for infants, and is easy to handle because it is easily deformed. Desired.

  In the medical field, a three-dimensional model of an organ model based on a three-dimensional image of an organ is used for a surgical operation plan, and is used as a practice organ model for increasing the skill level of a surgical operation. It is coming. In these models, it is desirable that the flexibility and elasticity are expressed in a form closer to that of an actual organ. Therefore, it is important to select a resin material used for three-dimensional modeling.

  For example, it is known to produce an optically shaped article having high flexibility and elasticity by irradiating a composition containing a specific urethane compound in an optical three-dimensional modeling method with ultraviolet rays (Japanese Patent Laid-Open No. 9-169827 (patent). Document 1), Japanese Patent Application Laid-Open No. 2000-290328 (Patent Document 2), Japanese Patent Application Laid-Open No. 2006-028499 (Patent Document 3) Also disclosed is a composition for optical three-dimensional modeling that has high heat resistance and high transparency (Japanese Patent Application Laid-Open No. 2000-290499 2000-204125 (patent document 4)).

In the manufacturing method of an optical modeling thing, since the light of the light to irradiate is 400 nm or more, since it is light of weak energy compared with an ultraviolet-ray, the versatility of a manufacturing apparatus will become high from a safety surface.
However, the compositions described in Patent Documents 1 to 4 have insufficient curability with light having a wavelength of 400 nm or more. Moreover, although the molded article obtained from the composition described in these patent documents shows a high tensile modulus, the adhesion with the container made of fluororesin is too high, and when removing the molded article from the container, The container could be damaged. (Patent Documents 1 to 3). Furthermore, although the molded article obtained from the composition described in Patent Document 4 shows a high tensile elastic modulus in a test according to JIS K7127, the elongation at break is as small as less than 10%, and the resulting molded article is flexible. Sex was insufficient.

Further, in the optical three-dimensional modeling method in which light is irradiated from above the support, the support is lowered into a container containing the photocurable composition for optical three-dimensional modeling, and the lamination is repeated, so that the resulting model is obtained. In large cases, a large amount of photocurable composition for optical three-dimensional modeling is required. On the other hand, in the optical three-dimensional modeling method of irradiating light from below the support, it is sufficient that only the exposed portion is immersed in the photocurable composition, so that a large amount of composition is not required.
However, since light is irradiated from the lower side of the support, the adhesion between the bottom surface of the container and the modeled object (cured product) has a certain level or more, so when removing the modeled object from the container, the modeled object and the container Could hurt.

JP-A-9-169827 JP 2000-290328 A JP 2006-028499 A JP 2000-204125 A

Under the above circumstances, there is a need for a photocurable composition for optical three-dimensional modeling that can be easily cured by irradiating with a light beam having a wavelength of 400 nm or more and that can easily remove the formed model from the container. ing.
In addition, the modeled object obtained by the optical three-dimensional modeling method has a versatile light that has a good performance balance between flexibility and elasticity, is not easily scratched, and can be easily deformed when handling the modeled object. There is a need for curable compositions.

  The present inventors include a radical polymerizable compound (A) represented by the formula (1), a photopolymerization initiator (B) that generates radicals upon irradiation with light having a wavelength of 400 nm or more, and a water-insoluble surfactant. It came to invent the photocurable composition for optical three-dimensional model | molding containing (C).

（式（１）中、Ｒ^１は式（２−１）または式（２−２）で表される構造を部分構造として含むａ価の有機基であり、Ｒ^２は水素または炭素数１〜６のアルキルであり、ａは２以上の整数である。）

波長が４００ｎｍ以上の光線の照射によりラジカルを発生する光重合開始剤（Ｂ）および、
非水溶性界面活性剤（Ｃ）
を含む光学的立体造形用光硬化性組成物であって、
当該光硬化性組成物に波長が４００ｎｍ以上の光線が照射されて得られる膜厚３０μｍの硬化膜の引張り試験による弾性率が１０〜５００ＭＰａであり、当該硬化膜の破断強度が１〜５０ＭＰａであり、当該硬化膜の破断伸度が１０〜１００％である、光硬化性組成物。
［２］
光重合開始剤（Ｂ）がα-アミノアルキルフェノン系およびアシルフォスフィンオキサイド系化合物からなる群から選ばれる１以上である、［１］に記載の光硬化性組成物。
［３］
非水溶性界面活性剤（Ｃ）がフッ素系界面活性剤およびシリコーン系界面活性剤からなる群から選ばれる１以上である、［１］または［２］に記載の光硬化性組成物。
［４］
さらに、式（３）で表される構造を有し、ラジカル重合性化合物（Ａ）とは異なる構造のその他のラジカル重合性化合物（Ｄ）を含む、［１］〜［３］のいずれかに記載の光硬化性組成物。

（式（３）中、Ｒ^３はＣＨ_２＝ＣＨ−ＣＯ−を有しない１価の有機基、Ｒ^４は水素または炭素数１〜６のアルキルである。）
［５］
その他のラジカル重合性化合物（Ｄ）のＲ^３が式（４）で表される構造を有する化合物である、［４］に記載の光硬化性組成物。

（式（４）中、Ｒ^５は環状構造を有してよい２価の有機基である）
［６］
［１］〜［５］のいずれかに記載の光硬化性組成物に波長が４００ｎｍ以上の光線を照射する工程を含む、造形物の製造方法。
［７］
波長が４００ｎｍ以上の光線を支持体の下方向または水平方向から照射する、［６］に記載の製造方法。 [1]
Radical polymerizable compound represented by formula (1) (A)

(In the formula (1), R ¹ is an a-valent organic group containing the structure represented by the formula (2-1) or the formula (2-2) as a partial structure, and R ² is hydrogen or a carbon number of 1 to 1. 6 is an alkyl, and a is an integer of 2 or more.)

A photopolymerization initiator (B) that generates radicals upon irradiation with light having a wavelength of 400 nm or more; and
Water-insoluble surfactant (C)
Comprising a photocurable composition for optical three-dimensional modeling,
The elastic modulus of the cured film having a thickness of 30 μm obtained by irradiating the photocurable composition with light having a wavelength of 400 nm or more is 10 to 500 MPa, and the cured film has a breaking strength of 1 to 50 MPa. The photocurable composition whose breaking elongation of the said cured film is 10 to 100%.
[2]
The photocurable composition according to [1], wherein the photopolymerization initiator (B) is one or more selected from the group consisting of α-aminoalkylphenone compounds and acylphosphine oxide compounds.
[3]
The photocurable composition according to [1] or [2], wherein the water-insoluble surfactant (C) is one or more selected from the group consisting of a fluorine-based surfactant and a silicone-based surfactant.
[4]
Furthermore, any one of [1] to [3], which includes another radical polymerizable compound (D) having a structure represented by the formula (3) and having a structure different from the radical polymerizable compound (A). The photocurable composition as described.

(In Formula (3), R ³ is a monovalent organic group not having CH ₂ ═CH—CO—, and R ⁴ is hydrogen or alkyl having 1 to 6 carbon atoms.)
[5]
The photocurable composition according to [4], wherein R ^{3 of the} other radical polymerizable compound (D) is a compound having a structure represented by the formula (4).

(In formula (4), R ⁵ is a divalent organic group which may have a cyclic structure)
[6]
The manufacturing method of a molded article including the process of irradiating the light-curable composition in any one of [1]-[5] with a light ray with a wavelength of 400 nm or more.
[7]
The production method according to [6], wherein a light beam having a wavelength of 400 nm or more is irradiated from below or in the horizontal direction of the support.

  In the present specification, the “organic group” is not particularly limited, and examples thereof include a hydrocarbon group having 1 to 20 carbon atoms. Specific examples of the hydrocarbon group include aryl, alkylaryl, aryl Examples include alkyl, cycloalkyl, cycloalkenyl and the like.

Further, as the monovalent organic group, specifically, alkoxy having 1 to 20 carbon atoms which may have a substituent, aryloxy having 6 to 20 carbon atoms which may have a substituent, An optionally substituted amino, an optionally substituted silyl, an optionally substituted alkylthio (—SY ¹ , wherein Y ¹ has a substituent. May represent an alkyl having 1 to 20 carbon atoms.), An arylthio optionally having a substituent (-SY ² , wherein Y ² is an optionally substituted substituent having 6 to 18 carbon atoms. Aryl represents an aryl group), and optionally substituted alkylsulfonyl (—SO ₂ Y ³ , wherein Y ³ represents an optionally substituted alkyl group having 1 to 20 carbon atoms). , Optionally substituted arylsulfonyl (—SO ₂ Y ⁴ , wherein Y ⁴ is substituted An aryl having 6 to 18 carbon atoms which may have a group).

  In the present specification, the hydrocarbon group of the “C 1-20 hydrocarbon group” may be saturated or unsaturated acyclic, or may be saturated or unsaturated cyclic. When the hydrocarbon group having 2 to 20 carbon atoms is acyclic, it may be linear or branched. “C1-C20 hydrocarbon group” includes alkyl having 1 to 20 carbons, alkenyl having 2 to 20 carbons, alkynyl having 2 to 20 carbons, alkyldienyl having 4 to 20 carbons, carbon number Examples include aryl having 6 to 18 carbon atoms, alkyl aryl having 7 to 20 carbon atoms, arylalkyl having 7 to 20 carbon atoms, cycloalkyl having 4 to 20 carbon atoms, and cycloalkenyl having 4 to 20 carbon atoms.

  In the present specification, the “alkyl having 1 to 20 carbon atoms” is preferably alkyl having 1 to 10 carbon atoms, and more preferably alkyl having 1 to 6 carbon atoms. Examples of alkyl include, but are not limited to, methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl, t-butyl, pentyl, hexyl, dodecanyl and the like.

  In the present specification, “alkenyl having 2 to 20 carbon atoms” is preferably alkenyl having 2 to 10 carbon atoms, and more preferably alkenyl having 1 to 6 carbon atoms. Examples of alkenyl include, but are not limited to, vinyl, allyl, propenyl, isopropenyl, 2-methyl-1-propenyl, 2-methylallyl, 2-butenyl and the like.

  In the present specification, the “alkynyl having 2 to 20 carbon atoms” is preferably alkynyl having 2 to 10 carbon atoms, more preferably alkynyl having 2 to 6 carbon atoms. Examples of alkynyl include, but are not limited to, ethynyl, propynyl, butynyl and the like.

  In the present specification, “alkyl dienyl having 4 to 20 carbon atoms” is preferably alkyl dienyl having 4 to 10 carbon atoms, and more preferably alkyl dienyl having 4 to 6 carbon atoms. Examples of alkyldienyl include, but are not limited to, 1,3-butadienyl and the like.

  In the present specification, “aryl having 6 to 18 carbon atoms” is preferably aryl having 6 to 10 carbon atoms. Examples of aryl include, but are not limited to, phenyl, 1-naphthyl, 2-naphthyl, indenyl, biphenylyl, anthryl, phenanthryl and the like.

  In the present specification, the “alkyl aryl having 7 to 20 carbon atoms” is preferably alkyl aryl having 7 to 12 carbon atoms. Examples of alkylaryl include, but are not limited to, o-tolyl, m-tolyl, p-tolyl, 2,3-xylyl, 2,4-xylyl, 2,5-xylyl, o-cumenyl, m- Examples thereof include cumenyl, p-cumenyl, mesityl and the like.

  In the present specification, the “arylalkyl having 7 to 20 carbon atoms” is preferably arylalkyl having 7 to 12 carbon atoms. Examples of arylalkyl include, but are not limited to, benzyl, phenethyl, diphenylmethyl, triphenylmethyl, 1-naphthylmethyl, 2-naphthylmethyl, 2,2-diphenylethyl, 3-phenylpropyl, 4-phenyl Examples include butyl and 5-phenylpentyl.

  In the present specification, the “cycloalkyl having 4 to 20 carbon atoms” is preferably cycloalkyl having 4 to 10 carbon atoms. Examples of cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like.

  In the present specification, “cycloalkenyl having 4 to 20 carbon atoms” is preferably cycloalkenyl having 4 to 10 carbon atoms. Examples of cycloalkenyl include, but are not limited to, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl and the like.

  In the present specification, “C2-C20 alkoxy” is preferably C2-C10 alkoxy, and more preferably C2-C6 alkoxy. Examples of alkoxy include, but are not limited to, ethoxy, propoxy, butoxy, pentyloxy, and the like.

  In the present specification, “aryloxy having 6 to 20 carbon atoms” is preferably aryloxy having 6 to 10 carbon atoms. Examples of aryloxy include, but are not limited to, phenyloxy, naphthyloxy, biphenyloxy, and the like.

In the present specification, “alkylthio (—SY ¹ , wherein Y ¹ represents an optionally substituted alkyl having 2 to 20 carbon atoms)” and “alkylsulfonyl (—SO ₂ Y ³ , wherein , Y ³ represents an optionally substituted alkyl having 1 to 20 carbon atoms.) ”, Y ¹ and Y ³ are preferably alkyl having 2 to 10 carbon atoms, and 2 to 6 carbon atoms. More preferably, it is alkyl. Examples of alkyl include, but are not limited to, methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl, t-butyl, pentyl, hexyl, dodecanyl and the like.

In the present specification, “arylthio (—SY ² , wherein Y ² represents optionally substituted aryl having 6 to 18 carbon atoms)” and “arylsulfonyl (—SO ₂ Y ⁴ , wherein , Y ⁴ represents an optionally substituted aryl having 6 to 18 carbon atoms.) ”, Y ² and Y ⁴ are preferably aryl having 6 to 10 carbon atoms. Examples of aryl include, but are not limited to, phenyl, 1-naphthyl, 2-naphthyl, indenyl, biphenylyl, anthryl, phenanthryl and the like.

“C1-C20 hydrocarbon group”, “C1-C20 alkoxy”, “C6-C20 aryloxy”, “amino”, “silyl”, “alkylthio”, “arylthio”, “ A substituent may be introduced into “alkylsulfonyl”, “arylsulfonyl” and the like.
In the present specification, examples of the “substituent” include halogen (fluorine, chlorine, bromine, iodine, etc.), ester, carboxyl, amide, alkyne, trimethylsilyl, amino, phosphonyl, thio, carbonyl, nitro, sulfo, imino, Examples include halogeno and alkoxy. In this case, one or more substituents may be introduced at the substitutable position up to the maximum number that can be substituted, and preferably 1 to 4 substituents may be introduced. When the number of substituents is 2 or more, each substituent may be the same or different.

  In the present specification, examples of “amino optionally having a substituent” include, but are not limited to, amino, dimethylamino, methylamino, methylphenylamino, phenylamino and the like.

  In the present specification, examples of “optionally substituted silyl” include, but are not limited to, dimethylsilyl, diethylsilyl, trimethylsilyl, triethylsilyl, trimethoxysilyl, triethoxysilyl, diphenylmethyl. There are silyl, triphenylsilyl, triphenoxysilyl, dimethylmethoxysilyl, dimethylphenoxysilyl, methylmethoxyphenyl and the like.

  Specific examples of the monovalent organic group have been described above. In the present specification, specific examples of the divalent organic group include a valence of 1 in the monovalent organic group described in the present specification. The group which added one is mentioned. Similarly, in the present specification, specific examples of the trivalent organic group include groups obtained by further increasing the valence by two in the monovalent organic group described in the present specification. Specific examples of the group include groups in which the valence is further increased by three in the monovalent organic group described in the present specification.

In this specification, the “light beam having a wavelength of 400 nm or more” means a light beam having a wavelength of 400 nm or more that can generate an active species by decomposing a compound that generates an active species, for example, a light beam such as visible light. Is mentioned.
The photopolymerization initiator that can be used in the polymerization reaction is not particularly limited as long as it is a compound that generates radicals upon irradiation with light having a wavelength of 400 nm or more.

  In this specification, “(meth) acrylate” is used to indicate both or one of acrylate and methacrylate. The “(meth) acryloyl group” is used to indicate both or one of an acryloyl group and a methacryloyl group.

  In the present specification, the “photocurable composition for optical three-dimensional modeling” may be referred to as “photocurable composition” or “composition”.

The cured film obtained from the photocurable composition according to a preferred embodiment of the present invention has a high tensile elastic modulus, breaking strength and breaking elongation, and therefore has a good performance balance between flexibility and elasticity, and toughness. It is possible to form a molded article excellent in the above.
Moreover, since the modeling thing obtained from the photocurable composition of the preferable aspect of this invention can be easily removed from a container, a modeling thing and a container are not damaged. In particular, in the optical three-dimensional modeling method of irradiating light from below, since the adhesive strength is below a certain level between the modeled object and the bottom surface of the container, the obtained modeled object and the container are peeled without being damaged. Is possible.
Moreover, the photocurable composition of the preferable aspect of this invention can be hardened | cured easily by irradiation of the light ray whose wavelength is 400 nm or more. Therefore, the photocurable composition of the preferable aspect of this invention can produce a molded article by the optical versatile modeling method with high versatility so that it can be easily used even in general households.

The figure which shows an example of the optical three-dimensional modeling method

DESCRIPTION OF SYMBOLS 1 Photocurable composition for optical three-dimensional modeling 2 Container 3a Mask 3b Mask 4 Support body 5 Light beam with a wavelength of 400 nm or more 6a Cured layer 6b Cured layer 7 Bottom of container

1 Photocurable composition for optical three-dimensional modeling The photocurable composition for optical three-dimensional modeling of the present invention is a radical polymerizable compound (A) represented by the formula (1), which is irradiated with light having a wavelength of 400 nm or more. A photopolymerization initiator (B) that generates radicals and a water-insoluble surfactant (C) are included.
The photocurable composition for optical three-dimensional modeling is not limited to being colorless and transparent, and may be colored.
Hereinafter, each component will be described.

1.1 Radical polymerizable compound (A)
The radically polymerizable compound (A) of the present invention is a compound represented by the formula (1).
In the formula (1), a is an integer of 2 or more, preferably 2 to 20, more preferably 3 to 10, and particularly preferably 3 to 5.

In formula (1), R ¹ is preferably an organic group containing an alkylene oxide or caprolactone as a partial structure, and more preferably an organic group containing an alkylene oxide having 1 to 6 carbon atoms or caprolactone as a partial structure.

In the formula (1), R ² is hydrogen or alkyl having 1 to 6 carbons, particularly preferably hydrogen or alkyl having 1 carbon, and most preferably hydrogen.

  As the radical polymerizable compound (A), a commercially available product may be used, or a compound synthesized from an isocyanate compound, a hydroxyl group, and a compound having a (meth) acryloyl group may be used.

  Commercially available products of the radical polymerizable compound (A) include Bremer TA-604AU (trade name; NOF Corporation), New Frontier R1220, RST101, RST201, and R-1306X (tradename; Daiichi Kogyo Seiyaku). Co., Ltd.), purple light UV-3000B, 3310B, 7000B, 7600B (trade name; Nippon Synthetic Chemical Industry Co., Ltd.), 9893, 981, 964, 9013, 9001 (trade name; Arkema) Japan), Aronix M-215, 313, 315, 327 (trade name; Toagosei Co., Ltd.).

  The radical polymerizable compound (A) may be one type or a mixture of two or more types.

  When the content of the radically polymerizable compound (A) contained in the photocurable composition of the present invention is 3 to 96% by weight based on the total weight of the composition, it can be obtained by irradiation with light having a wavelength of 400 nm or more. It is preferable because flexibility and elasticity of the molded article are increased, more preferably 5 to 96% by weight, and further preferably 10 to 96% by weight.

1.2 Photopolymerization initiator (B)
The photopolymerization initiator (B) of the present invention is not particularly limited as long as it is a compound capable of generating radicals upon irradiation with light having a wavelength of 400 nm or more, but is not limited to α-aminoalkylphenone-based and acylphosphine-based compounds. A photopolymerization initiator is more preferable because the photocurability and storage stability of the photocurable composition are improved.

Specific examples of compounds capable of generating radicals upon irradiation with light having a wavelength of 400 nm or longer include 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl}. 2-methyl-1-propanone, 2- (dimethylamino) -1- (4-morpholinophenyl) -2-benzyl-1-butanone, 2- (dimethylamino) -2-[(4-methylphenyl) methyl ] -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone, bis (2,4,6- Trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (η ⁵ -2,4-si Clopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, 1- [4- (phenylthio) phenyl] -1,2-octanedione- 2- (O-benzoyloxime)].
Among these, α-aminoalkylphenone-based or acylphosphine-based compounds such as 2- (dimethylamino) -1- (4-morpholinophenyl) -2-benzyl-1-butanone and 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1 -Propanone, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide are preferred.

  The photopolymerization initiator (B) may be one type or a mixture of two or more types.

  The content of the photopolymerization initiator (B) is preferably 1 to 25 parts by weight with respect to 100 parts by weight of the total of the radical polymerizable compounds contained in the composition, because photocurability is excellent, and more preferably 3 -20 parts by weight, more preferably 5-15 parts by weight.

1.3 Water-insoluble surfactant (C)
The water-insoluble surfactant (C) of the present invention is not particularly limited as long as it is a water-insoluble surfactant, but has good compatibility with other components contained in the photocurable composition of the present invention. Compounds are preferred. Moreover, it is preferable that it is a compound which does not affect the softness | flexibility and elasticity of a molded article obtained from a photocurable composition, and can improve the mold release property of the molded article obtained from this photocurable composition.

  The water-insoluble surfactant (C) is preferably a non-ionic surfactant, and particularly preferably a water-insoluble fluorine-based surfactant and a water-insoluble silicone-based surfactant.

  Specific examples of the water-insoluble surfactant (C) include Megafac RS-72K, F-444, F-555 (trade name; DIC Corporation), TEGO Rad2200N, 2250, 2500, 2600, 2700 (trade name; Evonik Degussa Japan Co., Ltd.), BYK-306, 310, 315, 322, 370, 377, 3550, UV 3500 (trade name; Big Chemie Japan ( Etc.).

  The water-insoluble surfactant (C) used in the photocurable composition of the present invention may be one type or a mixture of two or more types.

In addition, the content of the water-insoluble surfactant (C) is preferably 0.05 to 5% by weight based on the total weight of the composition, and is preferably excellent in releasability from the container, more preferably 0. 0.1 to 5% by weight, particularly preferably 0.5 to 5% by weight.

1.4 Other radically polymerizable compounds (D)
The other radically polymerizable compound (D) of the present invention is not limited as long as it is a compound represented by the formula (3) and is not a radically polymerizable compound (A).

In formula (3), R ⁴ is hydrogen or alkyl having 1 to 6 carbon atoms, preferably hydrogen or alkyl having 1 to 3 carbon atoms, more preferably hydrogen or alkyl having 1 carbon atom. Hydrogen is most preferred.

In formula (4), R ⁵ is a divalent organic group which may have a cyclic structure, but is preferably a divalent organic group having 2 to 20 carbon atoms, and is a divalent group having 4 to 15 carbon atoms. More preferably, it is an organic group.
Specific examples of the compound having a structure in which R ³ of the compound (D) is represented by the formula (4) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl. (Meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, hydroxyphenyl (meth) acrylate, isocyanuric acid ethylene oxide modified di (meth) acrylate, glycerol di Examples include (meth) acrylate, pentaerythritol di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol penta (meth) acrylate.

  Other specific compounds of the radical polymerizable compound (D) other than these include n-butyl (meth) acrylate, t-butyl (meth) acrylate, γ-butyrolactone (meth) acrylate, tetrahydrofurfuryl (meta ) Acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, polyoxyethylene mono (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol Examples include hexa (meth) acrylate.

  The other radically polymerizable compound (D) of the present invention is appropriately used in order to adjust the viscosity of the composition within a range that does not impair the flexibility and elasticity of the shaped article obtained from the composition.

  The other radical polymerizable compound (D) may be one type or a mixture of two or more types.

  The content of the other radically polymerizable compound (D) is preferably 10 to 90% by weight, more preferably 20 to 80% by weight, still more preferably 25 to 75% by weight, based on the total weight of the composition. is there.

1.5 Other Additives The photocurable composition of the present invention can contain additives that can be mixed uniformly without departing from the spirit of the present invention. Specifically, the photocurable composition includes various solvents, polymerization inhibitors, plasticizers, antioxidants, ultraviolet absorbers, antistatic agents, flame retardants, flame retardant aids, fillers, pigments, dyes, and the like. Additives can be included.

  The photocurable composition of the present invention may contain a polymerization inhibitor in order to improve storage stability without departing from the spirit of the present invention. Specific examples of the polymerization inhibitor include 4-methoxyphenol, hydroquinone and phenothiazine. Among these, phenothiazine is preferable because the increase in viscosity is small even during long-term storage.

  The polymerization inhibitor used in the photocurable composition of the present invention may be one type or a mixture of two or more types.

  When the content of the polymerization inhibitor is 0.01 to 1 part by weight with respect to 100 parts by weight of the total of the photocurable compounds contained in the photocurable composition, the increase in viscosity is small even during long-term storage. Therefore, considering the balance with photocurability, it is more preferably 0.01 to 0.5 part by weight, and still more preferably 0.01 to 0.2 part by weight.

1.6 Preparation method of photocurable composition for optical three-dimensional model | molding of this invention The photocurable composition of this invention can be prepared by mixing each component used as a raw material by a well-known method.
In particular, the photocurable composition of the present invention is prepared by mixing the components (A) to (C) and other components as necessary, and filtering and degassing the resulting solution. Is preferred. For the filtration, for example, a fluororesin membrane filter is used.

  For the photocurable composition for optical three-dimensional modeling of the present invention thus obtained, a three-dimensional model having a desired shape is obtained by an optical three-dimensional modeling method of irradiating a predetermined pattern with a light beam having a wavelength of 400 nm or more. Is obtained.

1.7 Storage of Photocurable Composition of the Present Invention When the photocurable composition of the present invention is stored at 5 to 25 ° C., the viscosity change during storage is small, so that the storage stability is good.

2. Manufacturing method of modeling object The modeling object of this invention can be modeled by optical three-dimensional modeling methods, such as a well-known optical lamination modeling method. The optical three-dimensional modeling method will be described with reference to FIG.

As shown in FIG. 1 (A), the photocurable composition 1 is accommodated in a container 2, and the support 4 is movable up and down so that the stage of the support 4 is submerged under the liquid surface of the photocurable composition 1. Is installed. The bottom surface 7 of the container is a transparent material that transmits light having a wavelength of 400 nm or more, and the material is not particularly limited. For example, glass, fluororesin such as polytetrafluoroethylene (hereinafter referred to as “PTFE”), silicone, and the like Resins, metals and the like can be mentioned. Alternatively, a composite material in which a PTFE sheet or the like is bonded onto a transparent material may be used.
Next, as shown to FIG. 1 (B), the mask 3a is installed in the downward direction of a container based on the shape of the molded article manufactured. When the light beam 5 having a wavelength of 400 nm or more is irradiated from below the mask 3, the light beam 5 having a wavelength of 400 nm or more not blocked by the mask 3 a reaches the photocurable composition 1 in the container 2 and is cured and cured. The layer 6a is formed on the lower surface of the stage of the support 4 (first layer forming step).
Thereafter, as shown in FIG. 1C, the support body 4 is raised, and the mask 3b is installed based on the shape of the manufactured object to be manufactured. When a light beam 5 having a wavelength of 400 nm or more is irradiated from below the mask 3b, the light beam 5 having a wavelength of 400 nm or more not blocked by the mask 3b reaches the photocurable composition 1 in the container 2 and is cured. The layer 6b is formed below the hardened layer 6a (lamination process). By setting an area through which the light beam 5 having a wavelength of 400 nm or more is transmitted and irradiating the light beam 5 having a wavelength of 400 nm or more to cure the photocurable composition 1, a plurality of cured layers are integrated. A three-dimensional shaped object can be manufactured by being laminated on.

  The shape of the mask 3 used in the optical three-dimensional modeling method can be designed from cross-sectional group data obtained by slicing three-dimensional CAD data of a three-dimensional model to be modeled into a plurality of layers.

  The optical three-dimensional modeling method is a method of irradiating a light beam having a wavelength of 400 nm or more from the lower side of the container 2 and laminating a cured layer on the lower side of the stage of the support 4. The direction to perform is not limited to the downward direction of the container 2, and light having a wavelength of 400 nm or more may be irradiated from the lateral direction or upward direction of the container 2. For example, when a light beam having a wavelength of 400 nm or more is irradiated from above the container 2, the cured layer is stacked above the stage of the support 4, so that the stacking is performed while the support is set downward. Will repeat.

  The method for selectively irradiating the photocurable composition 1 with light having a wavelength of 400 nm or more is not limited to using the mask 3, and various means can be employed. For example, it is also possible to use a method of irradiating the photocurable composition 1 while scanning convergent light obtained using a laser beam, a lens, or the like.

  It is preferable to wash the shaped object after taking out the shaped object obtained by laminating the hardened layer from the container 2. Although the cleaning agent is not particularly limited, for example, ethanol is used.

The amount of light having an irradiation wavelength of 400 nm or more (exposure amount) is adjusted by the composition of the photocurable composition, the thickness of the cured layer to be formed by one irradiation, manufactured by Ushio Electric Co., Ltd. as measured by the light receiver UVD-405PD integrating actinometer UIT-201 fitted with a, preferably 10~1,000mJ / cm ^2, more preferably 10 to 500 mJ / cm ^2, more preferably 10 to 300 mJ / cm ² . Moreover, 400-550 nm is preferable and, as for the wavelength of the light ray to irradiate, 400-500 nm is more preferable.

The light source is not particularly limited as long as it is a device that emits light having a wavelength of 400 nm or more. For example, an LED, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, a halogen lamp, a xenon lamp, or the like can be used.

  By doing as mentioned above, it is possible to produce an optically shaped article with high flexibility and elasticity from the photocurable composition of the present invention, and it is possible to easily remove the shaped article from the container.

3 Modeling object The modeling object of the present invention can be manufactured by the above-described optical three-dimensional modeling method. That is, in the optical three-dimensional modeling method, after curing a specific portion of the photocurable composition of the present invention, the cured layer is laminated while moving the support and changing the light irradiation position (irradiation surface). By doing so, a three-dimensional shaped object is obtained. Therefore, the shaped article of the present invention is composed of a laminate of cured layers obtained by curing the photocurable composition for optical three-dimensional modeling.

  Although the size of the shaped article of the present invention is not particularly limited, it is usually a scale of several mm to several meters, typically several centimeters to several tens of centimeters.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited by these.

[Example 1]
As a radically polymerizable compound (A), Bremer TA-604AU (trade name; NOF Corporation, hereinafter referred to as “TA-604AU”), and DAROCUR TPO (trade name; BASF Japan ( ), Hereinafter referred to as “TPO”), as a water-insoluble surfactant (C), MegaFac RS-72K (trade name; DIC Corporation), which is a fluorine-based water-insoluble surfactant, hereinafter referred to as “RS-72K”. As the other radical polymerizable compound (D), 4-hydroxybutyl acrylate (trade name; Nippon Kasei Co., Ltd., hereinafter referred to as “4HBA”) is mixed and dissolved in the following composition. Then, it filtered with the membrane filter (5 micrometers) made from PTFE, and prepared the photocurable composition 1.
(A) TA-604AU 8.00g
(B) TPO 0.80g
(C) RS-72K 0.56g
(D) 4HBA 8.00g

  As a result of measuring the viscosity of the photocurable composition 1 at 25 ° C. using a TV-22 (trade name; Toki Sangyo Co., Ltd., hereinafter referred to as “TV-22”) of an E-type viscometer, it was 165 mPa · s. there were.

[Example 2]
As radically polymerizable compound (A), New Frontier RST101 (trade name; Daiichi Kogyo Seiyaku Co., Ltd., hereinafter referred to as “RST101”) was used, and the composition ratio was as follows. A curable composition 2 was prepared.

(A) RST101 8.00g
(B) TPO 0.80g
(C) RS-72K 0.56g
(D) 4HBA 8.00g

  It was 98 mPa * s as a result of measuring the viscosity of the photocurable composition 2 in 25 degreeC using TV-22.

[Example 3]
A photocurable composition 3 was prepared in the same manner as in Example 1 except that CN 9893 (trade name; manufactured by Arkema Japan) was used as the radical polymerizable compound (A) and the following composition ratio was used.
(A) CN9873 8.00 g
(B) TPO 0.80g
(C) RS-72K 0.56g
(D) 4HBA 8.00g

  It was 256 mPa * s as a result of measuring the viscosity of the photocurable composition 3 in 25 degreeC using TV-22.

[Example 4]
As the radical polymerizable compound (A), Aronix M-327 (trade name; Toagosei Co., Ltd., hereinafter referred to as “M-327”) was used, and the composition ratio was as follows. A photocurable composition 4 was prepared.
(A) M-327 12.00 g
(B) TPO 0.80g
(C) RS-72K 0.56g
(D) 4HBA 4.00 g

  It was 225 mPa * s as a result of measuring the viscosity of the photocurable composition 4 in 25 degreeC using TV-22.

[Example 5]
Example 1 except that 4HBA and light acrylate IB-XA (trade name; Kyoeisha Chemical Co., Ltd., hereinafter referred to as “IB-XA”) were used as the other radical polymerizable compound (D) and the composition ratio was as follows. In the same manner as above, a photocurable composition 5 was prepared.
(A) TA-604AU 6.00g
(B) TPO 0.85g
(C) RS-72K 0.60g
(D) 1.00 g of 4HBA
(D) IB-XA 10.00 g

  As a result of measuring the viscosity of the photocurable composition 5 at 25 ° C. using TV-22, it was 98 mPa · s.

[Example 6]
Photocurable composition 6 was prepared in the same manner as in Example 4 except that IB-XA was used as the other radical polymerizable compound (D) and the following composition ratio was used.
(A) M-327 8.00 g
(B) TPO 0.73g
(C) RS-72K 0.51 g
(D) IB-XA 6.50 g

  As a result of measuring the viscosity of the photocurable composition 6 at 25 ° C. using TV-22, it was 141 mPa · s.

[Example 7]
As the water-insoluble surfactant (C), Megafac F-444 (trade name; DIC Corporation, hereinafter referred to as “F-444”, which is a fluorine-based water-insoluble surfactant, solid content concentration: 100 wt%) A photocurable composition 7 was prepared in the same manner as in Example 1 except that the following composition ratio was used.
(A) TA-604AU 6.00g
(B) TPO 0.85g
(C) F-444 0.18 g
(D) 1.00 g of 4HBA
(D) IB-XA 10.00 g

  It was 98 mPa * s as a result of measuring the viscosity of the photocurable composition 7 in 25 degreeC using TV-22.

[Example 8]
As the water-insoluble surfactant (C), BYK-306 (trade name; Big Chemie Japan Co., Ltd., hereinafter referred to as “BYK-306”) which is a silicone-based water-insoluble surfactant. Solid content concentration: 12.5 wt %) Was used, and a photocurable composition 8 was prepared in the same manner as in Example 1 except that the composition ratio was as follows.
(A) TA-604AU 6.00g
(B) TPO 0.85g
(C) BYK-306 1.428 g
(D) 1.00 g of 4HBA
(D) IB-XA 10.00 g

  As a result of measuring the viscosity of the photocurable composition 8 at 25 ° C. using TV-22, it was 97 mPa · s.

[Example 9]
As a radically polymerizable compound (A), New Frontier R-1306X (trade name; Daiichi Kogyo Seiyaku Co., Ltd., hereinafter referred to as “R-1306X”), as a water-insoluble surfactant (C), fluorine-based water-insoluble A photocurable composition 9 was prepared in the same manner as in Example 1 except that F-444, which is a surfactant, was used and the composition ratio was as follows.
(A) R-1306X 8.00g
(B) TPO 0.80g
(C) F-444 0.17 g
(D) 4HBA 8.00g

  It was 189 mPa * s as a result of measuring the viscosity of the photocurable composition 9 in 25 degreeC using TV-22.

[Example 10]
A photocurable composition 10 was prepared in the same manner as in Example 9 except that 4HBA and IB-XA were used as the other radical polymerizable compound (D) and the following composition ratio was used.
(A) R-1306X 8.00g
(B) TPO 0.80g
(C) F-444 0.17 g
(D) 4HBA 4.00 g
(D) IB-XA 4.00 g

It was 232 mPa * s as a result of measuring the viscosity of the photocurable composition 10 in 25 degreeC using TV-22.

[Comparative Example 1]
Aronix M-305 (trade name; Toagosei Co., Ltd., hereinafter referred to as “M-305”), which is pentaerythritol triacrylate, is used as the other radical polymerizable compound (D) without using the radical polymerizable compound (A). A photocurable composition C1 was prepared in the same manner as in Example 1 except that 4HBA was used and the following composition ratio was used.
(B) TPO 0.80g
(C) RS-72K 0.56g
(D) 4HBA 4.00 g
(D) M-305 12.00 g

  As a result of measuring the viscosity of the photocurable composition C1 at 25 ° C. using TV-22, it was 109 mPa · s.

[Comparative Example 2]
A photocurable composition C2 was prepared in the same manner as in Example 5 except that the surfactant (C) was not used and the following composition ratio was used.
(A) TA-604AU 6.00g
(B) TPO 0.85g
(D) 1.00 g of 4HBA
(D) IB-XA 10.00 g

  As a result of measuring the viscosity of the photocurable composition C2 at 25 ° C. using TV-22, it was 100 mPa · s.

[Comparative Example 3]
1-Hydroxycyclohexyl phenyl ketone (BASF Japan Ltd., hereinafter referred to as “Irg184”), which is a photopolymerization initiator that does not generate radicals by irradiation with light having a wavelength of 400 nm or more without using a photopolymerization initiator (B). A photocurable composition C3 was prepared in the same manner as in Example 5 except that the following composition ratio was used.
(A) TA-604AU 6.00g
(C) RS-72K 0.60g
(D) 1.00 g of 4HBA
(D) IB-XA 10.00 g
Irg184 0.85g

  It was 98 mPa * s as a result of measuring the viscosity of the photocurable composition C3 in 25 degreeC using TV-22.

[Comparative Example 4]
As compound (A), purple light UV-7000B (trade name; Nippon Synthetic Chemical Industry Co., Ltd., hereinafter referred to as “UV-7000B”) was used in the same manner as in Example 1 except that the composition ratio was as follows. A photocurable composition C4 was prepared.
(A) UV-7000B 8.00 g
(B) TPO 0.80g
(C) RS-72K 0.56g
(D) 4HBA 8.00g

  It was 278 mPa * s as a result of measuring the viscosity of the photocurable composition C4 in 25 degreeC using TV-22.

[Comparative Example 5]
A photocurable composition C5 was prepared in the same manner as in Example 3 except that 4HBA and IB-XA were used as the other radical polymerizable compound (D) and the following composition ratio was used.
(A) CN9873 6.00 g
(B) TPO 0.90g
(C) RS-72K 0.63g
(D) 2.00 g of 4HBA
(D) IB-XA 10.00 g

  As a result of measuring the viscosity of the photocurable composition C5 at 25 ° C. using TV-22, it was 147 mPa · s.

[Comparative Example 6]
As a compound (A), New Frontier R1220 (trade name; Daiichi Kogyo Seiyaku Co., Ltd., hereinafter referred to as “R1220”) was used, and the composition ratio was as follows. Product C6 was prepared.
(A) R1220 8.00 g
(B) TPO 0.80g
(C) RS-72K 0.56g
(D) 4HBA 8.00g

  As a result of measuring the viscosity of the photocurable composition C6 at 25 ° C. using TV-22, it was 262 mPa · s.

[Comparative Example 7]
In place of the water-insoluble surfactant (C), MegaFac F-477 (trade name; DIC Corporation, hereinafter referred to as “F-477”) which is a fluorine-based water-soluble surfactant. Solid content concentration: 100 wt% The photocurable composition C7 was prepared in the same manner as in Example 5 except that the following composition ratio was used.
(A) TA-604AU 6.00g
(B) TPO 0.85g
(D) 1.00 g of 4HBA
(D) IB-XA 10.00 g
F-477 0.18g

  Since the photocurable composition C7 was suspended, the subsequent evaluation was stopped.

[Comparative Example 8]
Instead of the water-insoluble surfactant (C), BYK-342 (trade name; Big Chemie Japan Co., Ltd., solid content concentration: 53 wt%) which is a silicone-based water-soluble surfactant is used. Except that, a photocurable composition C8 was prepared in the same manner as in Example 5.
(A) TA-604AU 6.00g
(B) TPO 0.85g
(D) 1.00 g of 4HBA
(D) IB-XA 10.00 g
BYK-342 0.34g

  Since the photocurable composition C8 was suspended, the subsequent evaluation was stopped.

The structural formulas of M-327, 4HBA, IB-XA, TPO and Irg184 used in Examples and Comparative Examples were as follows.

[Evaluation of Photocurable Composition]
About the photocurable composition obtained by the said Example and comparative example, compatibility, photocurability, the tensile elasticity modulus of a cured film, breaking strength and breaking elongation, and peelability were evaluated as follows.

(1) Compatibility It was visually observed whether each component of the obtained photocurable composition was completely dissolved. The evaluation criteria are as follows.
○: Each component is dissolved, and the ink is transparent.
X: Some components are deposited and the ink is cloudy.

(2) Photocurability A 4 cm square glass substrate was prepared, 0.05 g of the photocurable composition was dropped on the glass substrate using a Pasteur pipette, and the glass substrate was stacked. Then, after h-ray transmission filter was further piled up, ultraviolet rays were irradiated using an ultraviolet ray irradiation device (TME-400PRC manufactured by Topcon Co., Ltd.). When the integrated exposure amount by the irradiation was measured with an integrated light meter UIT-201 equipped with a photoreceiver UVD-405PD manufactured by USHIO INC., It was 500 mJ / cm ² .
After irradiating with ultraviolet rays, one of the stacked glass substrates was peeled off, and the surface state of the cured film when the surface of the substrate was touched was observed with a microscope. The evaluation criteria are as follows.
○: No tactile marks remain on the surface of the cured film.
(Triangle | delta): A touching trace remains on the cured film surface.
×: Touch marks are completely left on the surface of the cured film.

(3) Tensile modulus, rupture strength, rupture elongation For UV curing equipment in which a photocurable composition is hung on a glass substrate with an aluminum foil attached, spin-coated (rotation speed: 300 rpm), and nitrogen-substituted. Stored in replacement box. Then, the h-ray transmission filter was piled up, and ultraviolet rays were irradiated using an ultraviolet ray irradiation device (TME-400PRC manufactured by Topcon Co., Ltd.). When the integrated exposure amount by the irradiation was measured with an integrated light meter UIT-201 equipped with a photoreceiver UVD-405PD manufactured by USHIO INC., It was 500 mJ / cm ² .
After irradiating with ultraviolet rays, the cured film was peeled off from the aluminum foil to prepare a test piece (5 mm × 25 mm × 30 μm). Then, the tensile elastic modulus (MPa), breaking strength (MPa), and elongation at break (%) were determined for the tensile properties of the cured film using EZ Graph (trade name; Shimadzu Corporation). The distance between chucks was set to 15 mm and the tensile speed was set to 5 mm / min.
The above test was conducted in accordance with ASTM D882.

(4) Peelability of cured product from PTFE sheet 0.05 g of the photocurable composition was hung on a glass substrate on which the PTFE sheet had been pasted, and stored in a substitution box for an ultraviolet curing device substituted with nitrogen. Thereafter, the h-ray transmission filter was overlapped, and UV irradiation was performed using an ultraviolet irradiation device (TME-400PRC manufactured by Topcon Co., Ltd.). When the integrated exposure amount by the irradiation was measured with an integrated light meter UIT-201 equipped with a photoreceiver UVD-405PD manufactured by USHIO INC., It was 500 mJ / cm ² . The cured product formed on PTFE after irradiation with ultraviolet rays was picked with tweezers, and the peel resistance from the PTFE sheet was examined. The evaluation criteria are as follows.
(Double-circle): Hardened | cured material peels even if almost no force is applied.
○: If a force is applied to the extent that the cured product is not damaged, the cured product will be peeled off.
X: Hardened | cured material does not peel even if force is applied.

As is clear from the results shown in Table 1, the photocurable compositions 1 to 10 had good ink compatibility and photocuring.
Moreover, the cured film obtained by curing the photocurable compositions 1 to 10 shows values in the range of tensile modulus of 10 to 500 MPa, breaking strength of 1 to 50 MPa, and breaking elongation of 10 to 100%. ,It was good. Moreover, the peelability of these cured products from the PTFE sheet was also good.

  The cured product obtained by curing the photocurable composition for optical three-dimensional modeling of the present invention by an optical three-dimensional modeling method can be used for organ models in medical fields, prototypes of parts made of engineering plastics, and the like. .

Claims (7)

Radical polymerizable compound represented by formula (1) (A)

(In the formula (1), R ¹ is an a-valent organic group containing the structure represented by the formula (2-1) or the formula (2-2) as a partial structure, and R ² is hydrogen or a carbon number of 1 to 1. 6 is an alkyl, and a is an integer of 2 or more.)

A photopolymerization initiator (B) that generates radicals upon irradiation with light having a wavelength of 400 nm or more; and
Water-insoluble surfactant (C)
Comprising a photocurable composition for optical three-dimensional modeling,
The elastic modulus of the cured film having a thickness of 30 μm obtained by irradiating the photocurable composition with light having a wavelength of 400 nm or more is 10 to 500 MPa, and the cured film has a breaking strength of 1 to 50 MPa. The photocurable composition whose breaking elongation of the said cured film is 10 to 100%.   The photocurable composition according to claim 1, wherein the photopolymerization initiator (B) is one or more selected from the group consisting of an α-aminoalkylphenone-based compound and an acylphosphine oxide-based compound.   The photocurable composition according to claim 1 or 2, wherein the water-insoluble surfactant (C) is at least one selected from the group consisting of a fluorochemical surfactant and a silicone-based surfactant. Furthermore, it has the structure represented by Formula (3), and contains the other radically polymerizable compound (D) of the structure different from a radically polymerizable compound (A), The any one of Claims 1-3 Photocurable composition.

(In Formula (3), R ³ is a monovalent organic group not having CH ₂ ═CH—CO—, and R ⁴ is hydrogen or alkyl having 1 to 6 carbon atoms.) The photocurable composition according to claim 4, wherein R ^{3 of the} other radical polymerizable compound (D) is a compound having a structure represented by the formula (4).

(In formula (4), R ⁵ is a divalent organic group which may have a cyclic structure)   The manufacturing method of a molded article including the process of irradiating the photocurable composition in any one of Claims 1-5 with the light ray whose wavelength is 400 nm or more.   The manufacturing method of Claim 6 which irradiates the light ray whose wavelength is 400 nm or more from the downward direction or horizontal direction of a support body.

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