TW201439182A - Photo-curable composition for optical stereolithography and fabricating method of shape article - Google Patents

Abstract

A photo-curable composition for optical stereolithography includes: (A) a radical polymerization compound, (B) a photo-polymerization initiator which generates radicals by irradiating a light having a wavelength of 400 nm or more, (C) a water insoluble surfactant, whereby an elastic modulus of a tensile test of a curing film with a film thickness of 30 μ m obtained by irradiating a light having a wavelength of 400 nm or more to the photo-curable composition is 10 to 500 MPa, a breaking strength of the curing film is 1 to 50 MPa, and a breaking elongation of the curing film is 10 to 100%.

Description

Photocurable composition for optical three-dimensional modeling, and method for producing shaped object

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

As a method of manufacturing a three-dimensional shaped object, a method of manufacturing a three-dimensional shaped object by an optical three-dimensional modeling method such as an optical layering method has been proposed. For example, an optical three-dimensional modeling method is known in which each layer is formed based on data of a section group obtained by forming a three-dimensional CAD data slice of a stereoscopic mode into a plurality of layers, and the layers are integrally laminated. And make a three-dimensional shape.

One embodiment of the optical three-dimensional molding method can be carried out by repeatedly performing the following steps (1) and (2): (1) Selectively above the self-supporting body for the photocurable resin composition contained in the container Light such as a laser is irradiated to form a hardened layer having a predetermined pattern; and (2) the support is lowered by one layer.

As described above, the optical stereoscopic modeling method is used to repeatedly form the previous formation. The upper side of the hardened layer integrally forms a new hardened layer, whereby a three-dimensional shaped object in which a plurality of hardened layers are integrally formed can be manufactured.

In recent years, studies on the reduction in size, weight, and cost of an apparatus for manufacturing these three-dimensional shaped objects have required an inexpensive device that can be used on a tabletop even in a general household. In the optical three-dimensional shape used in the general household, it is required to have a wide range of characteristics such as difficulty in attaching a flaw to the molded article, softness of the molded article, high safety to the infant, and easy deformation, so that the operation of the molded article is easy.

Further, in the medical field, an organ model for stereoscopic modeling based on a three-dimensional image for photographing an organ is applied to a surgical operation plan for surgery, or an exercise organ model for improving the proficiency of surgery is applied. In these models, it is desirable to express softness and elasticity in a form closer to an actual organ, and therefore selection of a resin material used in a three-dimensional shape becomes important.

For example, it is known that a composition containing a specific urethane compound is irradiated with ultraviolet rays in an optical three-dimensional molding method, thereby producing a light-shaped material having high flexibility and elasticity (Japanese Patent Laid-Open No. Hei 9-169827 (Patent Document 1), Japanese Patent Laid-Open No. 2000-290328 (Patent Document 2), and Japanese Patent Laid-Open No. 2006-028499 (Patent Document 3)). Further, an optical three-dimensional molding composition having high heat resistance and transparency has been disclosed (Japanese Patent Laid-Open Publication No. 2000-204125 (Patent Document 4)).

In the method of producing a light-formed object, when the wavelength of the light to be irradiated is 400 nm or more, the energy is weak compared with the ultraviolet light. Therefore, the versatility of the manufacturing apparatus is increased from the viewpoint of safety and the like.

However, in the compositions described in Patent Documents 1 to 4, the wavelength is When the light is 400 nm or more, the hardenability is not sufficient. Further, the molded article obtained from the composition described in the above-mentioned patent documents exhibits a high value in tensile elastic modulus, but has high adhesion to a container containing a fluororesin, and when the molded article is taken out from the container, The container may be damaged (Patent Document 1 to Patent Document 3). In addition, the molded article obtained by the composition described in Patent Document 4 exhibits a high tensile modulus in the test based on JIS K7127, but the elongation at break is as small as less than 10%, and the obtained product is obtained. The softness of the shape is not sufficient.

Further, in the optical three-dimensional molding method in which the light is irradiated on the upper side of the self-supporting body, the support body is lowered into a container in which the optical stereolithic photocurable composition is placed, and the laminate is repeatedly laminated. In the large case, a large amount of optical stereolithic photocurable composition is required. On the other hand, in the optical three-dimensional molding method in which light is irradiated under the self-supporting body, it is sufficient that only the exposed portion is immersed in the curable composition, so that a large amount of the composition is not required.

However, in order to irradiate light from the lower side of the support body, a certain degree of adhesion force is formed between the bottom surface of the container and the molded object (cured material). Therefore, when the shaped object is taken out from the container, the shaped object may be The container caused damage.

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 9-169827

[Patent Document 2] Japanese Patent Laid-Open No. 2000-290328

[Patent Document 3] Japanese Patent Laid-Open No. 2006-028499

[Patent Document 4] Japanese Patent Laid-Open No. 2000-204125

Under the above circumstances, it is possible to use an optical stereolithic composition which can be easily cured by irradiating light having a wavelength of 400 nm or more, and which can easily take out the formed shaped object from the container.

In addition, the molded article obtained by the optical three-dimensional molding method requires a highly versatile photocurable composition which is excellent in balance between flexibility and elasticity, and which is less likely to cause damage and deformation during operation of the molded article.

The present inventors have invented a photopolymerization initiator (B) comprising a radical polymerizable compound (A) represented by the formula (1), a radical generated by irradiation of light having a wavelength of 400 nm or more, and a water-insoluble initiator (B). A photocurable composition for optical stereoscopic molding of the surfactant (C).

[1]

A photocurable composition comprising a radically polymerizable compound (A) represented by the formula (1), a photopolymerization initiator (B) which generates a radical by irradiation with light having a wavelength of 400 nm or more, and Photocurable composition for optical stereoscopic molding of water-insoluble surfactant (C),

(In the formula ^(1), R 1 comprising formula (2-1) or (2-2) structure represented as a partial structure a divalent organic group, R ² is hydrogen or alkyl having a carbon number of 1 to 6 Base, a is an integer of 2 or more)

The elastic modulus of the tensile test of the cured film having a film thickness of 30 μm obtained by irradiating the photocurable composition with light having a wavelength of 400 nm or more is 10 MPa to 500 MPa, and the rupture strength of the cured film is 1 MPa to 50 MPa. The elongation at break of the film is from 10% to 100%.

[2]

The photocurable composition according to the above [1], wherein the photopolymerization initiator (B) is one or more selected from the group consisting of an α-aminoalkylphenone-based compound and a fluorenylphosphine oxide-based compound. .

[3]

The photocurable composition according to the above [1], wherein the water-insoluble surfactant (C) is one selected from the group consisting of a fluorine-based surfactant and an anthrone-based surfactant. the above.

[4]

The photocurable composition according to any one of [1] to [3] further comprising another radical polymerizable compound (D), wherein the other radical polymerizable compound (D) has the formula (3) a structure represented, and the structure is different from the radically polymerizable compound (A);

(In the formula (3), R ³ is a monovalent organic group having no CH ₂ =CH-CO-, and R ⁴ is hydrogen or an alkyl group 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);

(Formula (4), R ⁵ is a divalent organic group may have a cyclic structure).

[6]

A method of producing a molded article, comprising the step of irradiating light having a wavelength of 400 nm or more with the photocurable composition according to any one of [1] to [5].

[7]

The production method according to [6], wherein the light having a wavelength of 400 nm or more is irradiated from the lower side or 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, and specific examples of the hydrocarbon group include an aryl group, an alkylaryl group, an arylalkyl group, a cycloalkyl group, and a ring. Alkenyl and the like.

Further, specific examples of the monovalent organic group include an alkoxy group having 1 to 20 carbon atoms which may have a substituent, and an aryloxy group having 6 to 20 carbon atoms which may have a substituent, and may have a substitution. a group of an amine group, a decyl group which may have a substituent, or an alkylthio group which may have a substituent (-SY ¹ , wherein Y ¹ represents an alkyl group having 1 to 20 carbon atoms which may have a substituent) And an arylthio group having a substituent (-SY ² , wherein Y ² represents an aryl group having 6 to 18 carbon atoms which may have a substituent), and an alkylsulfonyl group which may have a substituent ( -SO ₂ Y ³ , wherein Y ³ represents an alkyl group having 1 to 20 carbon atoms which may have a substituent, and an arylsulfonyl group which may have a substituent (-SO ₂ Y ⁴ , wherein Y ⁴ represents an aryl group having a carbon number of 6 to 18 which may have a substituent.

In the present specification, the hydrocarbon group of "hydrocarbon group having 1 to 20 carbon atoms" may be a saturated or unsaturated acyclic group, and may be a saturated or unsaturated ring type. When the hydrocarbon group having 2 to 20 carbon atoms is acyclic, it may be linear or branched. The "hydrocarbon group having 1 to 20 carbon atoms" includes an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, and an alkyl group having 4 to 20 carbon atoms. a dienyl group, an aryl group having 6 to 18 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, a cycloalkyl group having 4 to 20 carbon atoms, and carbon The number is 4 to 20 cycloalkenyl groups and the like.

In the present specification, the "alkyl group having 1 to 20 carbon atoms" is preferably a carbon number. It is an alkyl group of 1 to 10, more preferably an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group are not limited, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, a second butyl group, a tert-butyl group, a pentyl group, a hexyl group, and a dodecyl group.

In the present specification, the "alkenyl group having 2 to 20 carbon atoms" is preferably an alkenyl group having 2 to 10 carbon atoms, more preferably an alkenyl group having 1 to 6 carbon atoms. Examples of the alkenyl group are not limited, and examples thereof include a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a 2-methyl-1-propenyl group, a 2-methylallyl group, and a 2-butenyl group.

In the present specification, the "alkynyl group having 2 to 20 carbon atoms" is preferably an alkynyl group having 2 to 10 carbon atoms, more preferably an alkynyl group having 2 to 6 carbon atoms. Examples of the alkynyl group are not limited, and examples thereof include an ethynyl group, a propynyl group, a butynyl group and the like.

In the present specification, the "alkyldienyl group having 4 to 20 carbon atoms" is preferably an alkyldienyl group having 4 to 10 carbon atoms, more preferably an alkyl group having 4 to 6 carbon atoms. Alkenyl. Examples of the alkyldienyl group are not limited, and examples thereof include a 1,3-butadienyl group and the like.

In the present specification, the "aryl group having 6 to 18 carbon atoms" is preferably an aryl group having 6 to 10 carbon atoms. Examples of the aryl group are not limited, and examples thereof include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, an anthracenyl group, a biphenyl group, a fluorenyl group, and a phenanthryl group.

In the present specification, the "alkylaryl group having 7 to 20 carbon atoms" is preferably an alkylaryl group having 7 to 12 carbon atoms. Examples of the alkylaryl group are not limited, and examples thereof include o-tolyl, m-tolyl, p-tolyl, 2,3-xylyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, ortho Alkenyl, m-cumenyl, p-cumenyl, mesitylylene, and the like.

In the present specification, the "arylalkyl group having 7 to 20 carbon atoms" is preferably an arylalkyl group having 7 to 12 carbon atoms. Examples of the arylalkyl group are not limited, and benzyl may be mentioned. Base, phenethyl, diphenylmethyl, triphenylmethyl, 1-naphthylmethyl, 2-naphthylmethyl, 2,2-diphenylethyl, 3-phenylpropyl, 4 -phenylbutyl, 5-phenylpentyl and the like.

In the present specification, the "cycloalkyl group having 4 to 20 carbon atoms" is preferably a cycloalkyl group having 4 to 10 carbon atoms. Examples of the cycloalkyl group are not limited, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and the like.

In the present specification, the "cycloalkenyl group having 4 to 20 carbon atoms" is preferably a cycloalkenyl group having 4 to 10 carbon atoms. Examples of the cycloalkenyl group are not limited, and examples thereof include a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, and a cyclohexenyl group.

In the present specification, the "alkoxy group having 2 to 20 carbon atoms" is preferably an alkoxy group having 2 to 10 carbon atoms, more preferably an alkoxy group having 2 to 6 carbon atoms. Examples of the alkoxy group are not limited, and an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group or the like is present.

In the present specification, the "aryloxy group having 6 to 20 carbon atoms" is preferably an aryloxy group having 6 to 10 carbon atoms. Examples of the aryloxy group are not limited, and examples thereof include a phenoxy group, a naphthyloxy group, and a biphenyloxy group.

In the present specification, "alkylthio (-SY ¹ , wherein Y ¹ represents an alkyl group having 2 to 20 carbon atoms which may have a substituent)" and "alkylsulfonyl (-SO ₂ Y ^{3 )} In the formula, Y ³ represents an alkyl group having 1 to 20 carbon atoms which may have a substituent, and Y ¹ and Y ^{3 are} preferably an alkyl group having 2 to 10 carbon atoms, more preferably carbon. The number is 2 to 6 alkyl groups. Examples of the alkyl group are not limited, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, a second butyl group, a tert-butyl group, a pentyl group, a hexyl group, and a dodecyl group.

In the present specification, "arylthio (-SY ² , wherein Y ² represents an aryl group having 6 to 18 carbon atoms which may have a substituent)" and "arylsulfonyl (-SO ₂ Y ⁴⁾ formula, Y ⁴ represents a substituent having a carbon number may also be an aryl group having 6 to 18) "in, Y ² and Y ⁴ carbon atoms is preferably an aryl group having 6 to 10. Examples of the aryl group are not limited, and examples thereof include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, an anthracenyl group, a biphenyl group, a fluorenyl group, and a phenanthryl group.

"Carbon group having 1 to 20 carbon atoms", "alkoxy group having 1 to 20 carbon atoms", "aryloxy group having 6 to 20 carbon atoms", "amine group", "decyl group", "alkane" A substituent may be introduced into a sulfur group, an "arylthio group", an "alkylsulfonyl group", an "arylsulfonyl group" or the like.

In the present specification, examples of the "substituent" include halogen (such as fluorine, chlorine, bromine, and iodine), an ester, a carboxyl group, a decylamino group, an alkynyl group, a trimethyldecyl group, an amine group, a phosphonium group, and a thio group. A carbonyl group, a nitro group, a sulfonic acid group, an imido group, a halogenated group, or an alkoxy group. In this case, the substituent may be introduced at one or more positions up to the maximum number that can be substituted, and it is preferred to introduce one to four. When the number of substituents is two or more, each substituent may be the same or different.

In the present specification, the "amino group which may have a substituent" is not limited, and an amine group, a dimethylamino group, a methylamino group, a methylphenylamino group, a phenylamino group or the like may be present.

In the present specification, the example of the "nonyl group which may have a substituent" is not limited, and there are dimethyl decyl group, diethyl decyl group, trimethyl decyl group, triethyl decyl group, trimethoxy group.矽alkyl, triethoxyalkyl, diphenylmethyl decyl, triphenyl decyl, triphenyloxy decyl, dimethyl methoxy decyl, dimethyl phenoxy decyl, A Methoxy phenyl and the like.

Specific examples of the monovalent organic group are listed above, and specific examples of the divalent organic group in the present specification include the monovalent organic group described in the present specification. Add a base of 1 valence in one step. In the same manner, specific examples of the trivalent organic group in the present specification include a group in which two valences are further added to the monovalent organic group described in the present specification, and specific examples of the tetravalent organic group are exemplified in the present specification. Further, a base of three valences is added to the monovalent organic group described in the above.

In the present specification, the term "light having a wavelength of 400 nm or more" refers to light having a wavelength at which the active material is decomposed to generate an active material having a wavelength of 400 nm or more, and examples thereof include light rays such as visible light.

The photopolymerization initiator to be used in the polymerization reaction is not particularly limited as long as it is a compound which generates a radical by irradiation with light having a wavelength of 400 nm or more.

In the present specification, "(meth) acrylate" is used to mean either or both of an acrylate and a methacrylate. Further, "(meth)acrylonitrile" is used to mean either or both of an acryloyl group and a methacryl group.

In the present specification, the "photocurable composition for optical three-dimensional molding" may be referred to as "photocurable composition" or "composition".

Since the cured film obtained from the photocurable composition of the preferred embodiment of the present invention has a high tensile modulus, breaking strength, and elongation at break, it is possible to form a molded article having excellent balance between flexibility and elasticity and excellent toughness. .

Further, the molded article obtained from the photocurable composition of the preferred embodiment of the present invention can be easily taken out from the container, so that the molded article and the container are not damaged. In particular, in the optical three-dimensional modeling method in which light is irradiated from below, there is a certain degree of adhesion between the molded object and the bottom surface of the container, so that the resulting shape is not obtained. Peeling in the case where the object and the container cause damage.

Further, the photocurable composition of the preferred embodiment of the present invention can be easily cured by irradiation with light having a wavelength of 400 nm or more. Therefore, the photocurable composition of the preferred embodiment of the present invention can be produced by a highly versatile optical layering method which can be easily used in a general household.

1‧‧‧Optical stereolithic photocurable composition

2‧‧‧ Container

3a, 3b‧‧‧ mask

4‧‧‧Support

5‧‧‧Light with a wavelength above 400 nm

6a, 6b‧‧‧ hardened layer

7‧‧‧Bottom of the container

1(A) to 1(C) are diagrams showing an example of an optical three-dimensional modeling method.

1 Optical stereolithic photocurable composition

The photocurable composition for optical three-dimensional molding of the present invention comprises the radically polymerizable compound (A) represented by the formula (1) and a photopolymerization initiator which generates a radical by irradiation with light having a wavelength of 400 nm or more ( B), and a water-insoluble surfactant (C).

Further, the optical stereolithic photocurable composition 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 the formula (1), R ^{1 is} preferably an organic group containing an alkylene oxide or a caprolactone as a partial structure, more preferably an alkylene oxide having a carbon number of 1 to 6, or The ester serves as an organic group of a partial structure.

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

A commercially available product may be used as the radically polymerizable compound (A), and a compound obtained from an isocyanate compound and a compound having a hydroxyl group and a (meth)acryloyl group may be used.

Commercial products of the radical polymerizable compound (A) include BLEMMER TA-604AU (trade name; Nippon Oil Co., Ltd.), New frontier R1220, New frontier RST101, New frontier RST201, New frontier R-1306X (trade name; First Industrial Pharmaceutical Co., Ltd., Violet UV-3000B, Violet 3310B, Violet 7000B, Violet 7600B (trade name; Japan Synthetic Chemical Industry Co., Ltd.), the same as 9893, the same 981, the same 964, the same 9013, the same 9001 ( Trade name; Arkema Japan), ARONIX M-215, ARONIX 313, ARONIX 315, ARONIX 327 (trade name; East Asia Synthetic Co., Ltd.).

The radically polymerizable compound (A) may be used singly or in combination of two or more kinds.

When the content of the radically polymerizable compound (A) contained in the photocurable composition of the present invention is from 3% by weight to 96% by weight based on the total weight of the composition, the irradiation wavelength is 400 nm or more. The light of the resulting molded article is preferably softer and more elastic, and is more preferably from 5% by weight to 96% by weight, still more preferably from 10% by weight 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 can generate a radical by irradiation with light having a wavelength of 400 nm or more, and the α-aminoalkylphenone and the mercaptophosphine are. The photopolymerization initiator is more preferable because it can improve photocurability and preservability of the photocurable composition.

Specific examples of the compound which can generate a radical by irradiation with light having a wavelength of 400 nm or more include 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propenyl)-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-trimethylbenzylidene)-phenylphosphine oxide, 2,4,6- trimethyl benzoyl group - diphenyl - phosphine oxide, bis (η ⁵ -2,4- cyclopentadien-1-yl) - bis (2,6-difluoro-3- (lH-pyrrol - 1-yl)-phenyl)titanium, 1-[4-(phenylthio)phenyl]-1,2-octanedione-2-(O-benzoguanidinopurine).

Preferred among these are 2-(dimethylamino)-1-(4-morpholinophenyl)-2-benzyl which is an α-aminoalkylphenone or a mercaptophosphine compound. 1-butanone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butene Ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone, bis(2,4,6-trimethylbenzylidene)-phenyl Phosphine oxide, 2,4,6-trimethylbenzylidene-diphenyl-phosphine oxide.

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

The content of the photopolymerization initiator (B) is 1 part by weight to 25 parts by weight based on 100 parts by weight of the total of the radical polymerizable compound contained in the composition. The parts by weight are excellent in photocurability, and therefore more preferably 3 parts by weight to 20 parts by weight, still more preferably 5 parts by weight to 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, and it is preferred that the water-insoluble surfactant (C) is compatible with other components contained in the photocurable composition of the present invention. compound of. Further, a compound which does not affect the flexibility and elasticity of the molded article obtained from the photocurable composition, and which has improved mold release property of the molded article obtained from the photocurable composition, is preferable.

The water-insoluble surfactant (C) is preferably a nonionic surfactant, and particularly preferably a water-insoluble fluorine-based surfactant and a water-insoluble anthrone-based surfactant.

Specific examples of the water-insoluble surfactant (C) include Megafac RS-72K, Megafac F-444, Megafac F-555 (trade name; DIC), TEGO Rad 2200N, TEGO Rad 2250, and TEGO Rad 2500. TEGO Rad 2600, TEGO Rad 2700 (trade name; Evonik Degussa Japan), BYK-306, BYK-310, BYK-315, BYK-322, BYK-370, BYK-377 , BYK-3550, BYK-UV3500 (trade name; Japan BYK Chemical Co., Ltd.) and so on.

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.

Further, if the content of the water-insoluble surfactant (C) is from 0.05% by weight to 5% by weight based on the total weight of the composition, the release property from the container is excellent. It is preferably, more preferably, it is 0.1% by weight to 5% by weight, and particularly preferably 0.5% by weight to 5% by weight.

1.4 Other radical 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 compound of the radical polymerizable compound (A).

In the formula (3), R ⁴ is hydrogen or an alkyl group having 1 to 6 carbon atoms, preferably hydrogen or an alkyl group having 1 to 3 carbon atoms, more preferably hydrogen or an alkyl group having 1 carbon atom. The best is hydrogen.

In the formula (4), R ⁵ is a divalent organic group which may have a cyclic structure, preferably a divalent organic group having a carbon number of 2 to 20, more preferably a divalent organic group having a carbon number of 4 to 15. Organic base.

Specific examples of the compound in which R ³ of the compound (D) is a compound having a structure represented by the formula (4) include 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate. 4-hydroxybutyl (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, (methyl) Hydroxyphenyl acrylate, isomeric cyanuric acid ethylene oxide modified di(meth) acrylate, glycerol di(meth) acrylate, pentaerythritol di(meth) acrylate, trimethylolpropane Di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate.

Specific examples of the other radical polymerizable compound (D) other than these include n-butyl (meth)acrylate, tert-butyl (meth)acrylate, and γ-butyrolactone (meth)acrylate. Tetrahydrofurfuryl (meth)acrylate, cyclohexyl (meth)acrylate, Isobornyl (meth)acrylate, benzyl (meth)acrylate, polyoxyethylene mono(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, Dipentaerythritol hexa(meth) acrylate or the like.

The other radically polymerizable compound (D) of the present invention can be suitably used to adjust the viscosity of the composition within a range that does not impair the flexibility and elasticity of the molded article obtained from the composition.

The other radically polymerizable compound (D) may be used alone or in combination of two or more.

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

1.5 Other additives

The photocurable composition of the present invention may contain an additive which can be uniformly mixed within a range not departing from the gist of the present invention. Specifically, the photocurable composition may include various additives such as a solvent, a polymerization inhibitor, a plasticizer, an antioxidant, an ultraviolet absorber, an antistatic agent, a flame retardant, a flame retardant, a filler, a pigment, a dye, and the like. .

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

The polymerization inhibitor to be 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 from 0.01 part by weight to 1 part by weight based on 100 parts by weight of the total of the photocurable compound contained in the photocurable composition, the viscosity increases little even in long-term storage. Therefore, it is more preferable to use 0.01 parts by weight to 0.5 parts by weight, and more preferably 0.01 parts by weight to 0.2 parts by weight, in consideration of the balance with photocurability.

1.6 Method for preparing photocurable composition for optical three-dimensional modeling of the present invention

The photocurable composition of the present invention can be prepared by mixing various components which are raw materials by a known method.

Particularly preferably, the photocurable composition of the present invention can be prepared by mixing the above components (A) to (C) and optionally other components, and filtering and degassing the obtained solution. For the above filtration, for example, a membrane filter made of a fluororesin can be used.

The optical three-dimensional modeling method obtains a molded object having a desired shape, and the optical three-dimensional molding method irradiates the optical stereolithic photocurable composition of the present invention obtained as described above in a predetermined pattern. Light with a wavelength of 400 nm or more.

1.7 Preservation of the photocurable composition of the present invention

When the photocurable composition of the present invention is stored at 5 to 25 ° C, the change in viscosity during storage is small, so that the storage stability is good.

2 How to make shaped objects

The shaped object of the present invention can be optically formed by a known optical layering method or the like. Modeling and modeling. The optical three-dimensional modeling method will be described based on Fig. 1(A) to Fig. 1(C).

As shown in FIG. 1(A), the photocurable composition 1 is housed in the container 2, and the platform can be lifted and lowered so that the stage of the support 4 is submerged under the liquid surface of the photocurable composition 1. Body 4. The bottom surface 7 of the container is a transparent material that can transmit light having a wavelength of 400 nm or more, and the material is not particularly limited, and examples thereof include a fluororesin such as glass or polytetrafluoroethylene (hereinafter referred to as "PTFE"), an anthrone resin, and a metal. . Further, a composite material such as a PTFE sheet may be bonded to the transparent material.

Next, as shown in FIG. 1(B), the mask 3a is placed under the container based on the shape of the manufactured object. When the light 5 having a wavelength of 400 nm or more is irradiated from the lower side of the mask 3, the light 5 having a wavelength of 400 nm or less which is not blocked by the mask 3a reaches the photocurable composition 1 in the container 2, and is hardened and supported. The lower surface of the platform of the body 4 forms a hardened layer 6a (first layer forming step).

Thereafter, as shown in FIG. 1(C), the support 4 is raised, and the mask 3b is provided based on the shape of the manufactured object. When the light 5 having a wavelength of 400 nm or more is irradiated from the lower side of the mask 3b, the light 5 having a wavelength of 400 nm or more which is not blocked by the mask 3b reaches the photocurable composition 1 in the container 2, and is hardened and hardened. The lower side of the layer 6a forms a hardened layer 6b (layering step). In the region where the light 5 having a wavelength of 400 nm or more is transmitted, the step of irradiating the light 5 having a wavelength of 400 nm or more to cure the photocurable composition 1 is repeatedly performed, whereby a plurality of hardened layers can be integrally formed. The three-dimensional shape of the object.

The shape of the mask 3 used in the optical three-dimensional modeling method can be based on The three-dimensional CAD data slice of the stereoscopic mode of the modeling is designed as data of the obtained profile group of the plurality of layers.

The optical three-dimensional modeling method is a method of irradiating a light having a wavelength of 400 nm or more from the lower side of the container 2 to laminate a hardened layer under the platform of the support 4, and the direction of the light having a wavelength of 400 nm or more is not limited to the container 2 Below, light having a wavelength of 400 nm or more may be irradiated from the lateral direction and the upper side of the container 2. For example, when light having a wavelength of 400 nm or more is irradiated from above the container 2, a hardened layer is formed on the upper surface of the support 4, and thus the support is deposited while being deposited downward.

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

Preferably, the molded article obtained by laminating the hardened layer is taken out from the container 2, and then the molded article is washed. The cleaning agent is not particularly limited, and for example, ethanol is used.

The amount of light (exposure amount) of the wavelength of 400 nm or more to be irradiated can be adjusted according to the composition of the photocurable composition and the thickness of the hardened layer to be formed by one irradiation, and is manufactured by mounting a oxtail motor (strand). The photodetector UVD-405PD is measured by an integrated photometer UIT-201, preferably 10 mJ/cm ² to 1,000 mJ/cm ² , more preferably 10 mJ/cm ² to 500 mJ/cm ² , further preferably It is 10 mJ/cm ² to 300 mJ/cm ² . Further, the wavelength of the light to be irradiated is preferably from 400 nm to 550 nm, more preferably from 400 nm to 500 nm.

The light source is not particularly limited as long as it 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 carrying out as described above, a light-sensitive composition having high flexibility and elasticity can be produced from the photocurable composition of the present invention, and the molded article can be easily taken out from the container.

3 shape objects

The shaped object of the present invention can be produced by the above-described optical three-dimensional modeling method. In the optical three-dimensional molding method, after the specific portion of the photocurable composition of the present invention is cured, the support is moved while changing the irradiation position (irradiation surface) of the light to the one-layer hardened layer. A shaped object having a predetermined three-dimensional shape is obtained. Therefore, the molded article of the present invention includes a laminate of a hardened layer obtained by curing an optical stereolithic photocurable composition.

The size of the shaped object of the present invention is not particularly limited, but is usually from several mm to several m, and typically is a scale of several cm to several tens of cm.

[Examples]

Hereinafter, the present invention will be further illustrated by the examples, but the present invention is not limited to the examples.

[Example 1]

BLEMAMER TA-604AU (trade name; Nippon Oil Co., Ltd., hereinafter referred to as "TA-604AU") as a radical polymerization compound (A), and DAROCUR TPO (trade name) as a photopolymerization initiator (B) ; BASF Japan (shares), Hereinafter referred to as "TPO"), Megafac RS-72K (trade name; DIC), hereinafter referred to as "RS-72K", which is a fluorine-based water-insoluble surfactant of the water-insoluble surfactant (C). Solid content concentration: 30% by weight), 4-hydroxybutyl acrylate (trade name; Nippon Kasei Co., Ltd., hereinafter referred to as "4HBA") as another radical polymerizable compound (D), which is mixed and dissolved by the following composition Thereafter, the mixture was filtered through a membrane filter (5 μm) made of PTFE to prepare a photocurable composition 1.

(A) TA-604AU 8.00g

(B) TPO 0.80g

(C) RS-72K 0.56g

(D) 4HBA 8.00g

The viscosity of the photocurable composition 1 at 25 ° C was measured using an E-type viscometer TV-22 (trade name; Toki Sangyo Co., Ltd., hereinafter referred to as "TV-22"), and the result was 165 mPa. s.

[Embodiment 2]

The same procedure as in Example 1 was carried out except that the radical polymerizable compound (A) was used as the radical polymerizable compound (A) as the radical polymerizable compound (A). The photocurable composition 2 was prepared.

(A) RST101 8.00g

(B) TPO 0.80g

(C) RS-72K 0.56g

(D) 4HBA 8.00g

The viscosity of the photocurable composition 2 at 25 ° C was measured using TV-22, and the result was 98 mPa. s.

[Example 3]

The photocurable composition 3 was prepared in the same manner as in Example 1 except that the CN9893 (trade name; manufactured by Arkema Japan) was used as the radically polymerizable compound (A).

(A) CN9893 8.00g

(B) TPO 0.80g

(C) RS-72K 0.56g

(D) 4HBA 8.00g

The viscosity of the photocurable composition 3 at 25 ° C was measured using TV-22, and the result was 256 mPa. s.

[Example 4]

Aronix M-327 (trade name; East Asia Synthetic Co., Ltd., hereinafter referred to as "M-327") was used as the radical polymerizable compound (A) in the same manner as in Example 1 except that the following composition ratio was used. The photocurable composition 4 was prepared.

(A) M-327 12.00g

(B) TPO 0.80g

(C) RS-72K 0.56g

(D) 4HBA 4.00g

The viscosity of the photocurable composition 4 at 25 ° C was measured using TV-22, and the result was 225 mPa. s.

[Example 5]

4HBA and Light acrylate IB-XA (trade name; Kyoeisha Chemical Co., Ltd., hereinafter referred to as "IB-XA") are used as the other radical polymerizable compound (D), and the following composition ratio is used. The photocurable composition 5 was prepared in the same manner as in Example 1.

(A) TA-604AU 6.00g

(B) TPO 0.85g

(C) RS-72K 0.60g

(D) 4HBA 1.00g

(D) IB-XA 10.00g

The viscosity of the photocurable composition 5 at 25 ° C was measured using TV-22, and the result was 98 mPa. s.

[Embodiment 6]

The photocurable composition 6 was prepared in the same manner as in Example 4 except that IB-XA was used as the other radically polymerizable compound (D) in the following composition ratio.

(A) M-327 8.00g

(B) TPO 0.73g

(C) RS-72K 0.51g

(D) IB-XA 6.50g

The viscosity of the photocurable composition 6 at 25 ° C was measured using TV-22, and the result was 141 mPa. s.

[Embodiment 7]

A fluorine-based water-insoluble surfactant Megafac F-444 (trade name; DIC (hereinafter referred to as "F-444", solid content concentration: 100% by weight) was used as the water-insoluble surfactant (C). The photocurable composition 7 was prepared in the same manner as in Example 1 except for the following composition ratio.

(A) TA-604AU 6.00g

(B) TPO 0.85g

(C) F-444 0.18g

(D) 4HBA 1.00g

(D) IB-XA 10.00g

The viscosity of the photocurable composition 7 at 25 ° C was measured using TV-22, and the result was 98 mPa. s.

[Embodiment 8]

An indolone-based water-insoluble surfactant BYK-306 (trade name; Japan BYK Chemical Co., Ltd., hereinafter referred to as "BYK-306". Solid content concentration: 12.5 wt%) was used as the water-insoluble surfactant ( C) The 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 1.428g

(D) 4HBA 1.00g

(D) IB-XA 10.00g

The viscosity of the photocurable composition 8 at 25 ° C was measured using TV-22, and the result was 97 mPa. s.

[Embodiment 9]

A new frontier R-1306X (trade name; First Industrial Pharmaceutical Co., Ltd., hereinafter referred to as "R-1306X") was used as the radical polymerizable compound (A), and a fluorine-based water-insoluble surfactant F-444 was used. The photocurable composition 9 was prepared in the same manner as in Example 1 except that the water-insoluble surfactant (C) was used in the following composition ratio.

(A) R-1306X 8.00g

(B) TPO 0.80g

(C) F-444 0.17g

(D) 4HBA 8.00g

The viscosity of the photocurable composition 9 at 25 ° C was measured using TV-22, and the result was 189 mPa. s.

[Embodiment 10]

The photocurable composition 10 was prepared in the same manner as in Example 9 except that 4HBA and IB-XA were used as the other radically polymerizable compound (D) in the following composition ratio.

(A) R-1306X 8.00g

(B) TPO 0.80g

(C) F-444 0.17g

(D) 4HBA 4.00g

(D) IB-XA 4.00g

The viscosity of the photocurable composition 10 at 25 ° C was measured using TV-22, and the result was 232 mPa. s.

[Comparative Example 1]

The radical polymerizable compound (A) was not used, and pentaerythritol triacrylate ARONIX M-305 (trade name; East Asia Synthetic Co., hereinafter referred to as "M-305") and 4HBA were used as other radical polymerizable compounds ( D) The photocurable composition C1 was prepared in the same manner as in Example 1 except that the composition ratio was as follows.

(B) TPO 0.80g

(C) RS-72K 0.56g

(D) 4HBA 4.00g

(D)M-305 12.00g

The viscosity of the photocurable composition C1 at 25 ° C was measured using TV-22, and the result was 109 mPa. s.

[Comparative Example 2]

The photocurable composition C2 was prepared in the same manner as in Example 5 except that the surfactant (C) was not used.

(A) TA-604AU 6.00g

(B) TPO 0.85g

(D) 4HBA 1.00g

(D) IB-XA 10.00g

The viscosity of the photocurable composition C2 at 25 ° C was measured using TV-22, The result is 100mPa. s.

[Comparative Example 3]

The photopolymerization initiator (B) is not used, and 1-hydroxycyclohexyl phenyl ketone which is a photopolymerization initiator which does not generate radicals by irradiation with light having a wavelength of 400 nm or more is used (Japan BASF) The photocurable composition C3 was prepared in the same manner as in Example 5 except that the composition ratio was the same as that of the following composition ratio (hereinafter referred to as "Irg 184").

(A) TA-604AU 6.00g

(C) RS-72K 0.60g

(D) 4HBA 1.00g

(D) IB-XA 10.00g

Irg184 0.85g

The viscosity of the photocurable composition C3 at 25 ° C was measured using TV-22, and the result was 98 mPa. s.

[Comparative Example 4]

The same procedure as in Example 1 was carried out except that the compound (A) was used as the compound (A) in the form of the following composition ratio, using the UV-7000B (trade name; Nippon Synthetic Chemical Industry Co., Ltd., hereinafter referred to as "UV-7000B"). A photocurable composition C4 was prepared.

(A)UV-7000B 8.00g

(B) TPO 0.80g

(C) RS-72K 0.56g

(D) 4HBA 8.00g

The viscosity of the photocurable composition C4 at 25 ° C was measured using TV-22, The result is 278mPa. s.

[Comparative Example 5]

The photocurable composition C5 was prepared in the same manner as in Example 3 except that 4HBA and IB-XA were used as the other radically polymerizable compound (D) in the following composition ratio.

(A) CN9893 6.00g

(B) TPO 0.90g

(C) RS-72K 0.63g

(D) 4HBA 2.00g

(D) IB-XA 10.00g

The viscosity of the photocurable composition C5 at 25 ° C was measured using TV-22, and the result was 147 mPa. s.

[Comparative Example 6]

Photohardening was carried out in the same manner as in Example 1 except that New Frontier R1220 (trade name; First Industrial Pharmaceutical Co., Ltd., hereinafter referred to as "R1220") was used as the compound (A), and the following composition ratio was used. Sex composition C6.

(A) R1220 8.00g

(B) TPO 0.80g

(C) RS-72K 0.56g

(D) 4HBA 8.00g

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

[Comparative Example 7]

The fluorine-based water-soluble surfactant Megafac F-477 (trade name; DIC (share), hereinafter referred to as "F-477". solid content concentration: 100% by weight) was used instead of the water-insoluble surfactant (C). The photocurable composition C7 was prepared in the same manner as in Example 5 except for the following composition ratio.

(A) TA-604AU 6.00g

(B) TPO 0.85g

(D) 4HBA 1.00g

(D) IB-XA 10.00g

F-477 0.18g

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

[Comparative Example 8]

The indolinone-based water-soluble surfactant BYK-342 (trade name; Japan BYK Chemical Co., Ltd., solid content concentration: 53% by weight) was used instead of the water-insoluble surfactant (C), and the following composition ratio was used. The photocurable composition C8 was prepared in the same manner as in Example 5 except for the above.

(A) TA-604AU 6.00g

(B) TPO 0.85g

(D) 4HBA 1.00g

(D) IB-XA 10.00g

BYK-342 0.34g

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

The structural formulae of M-327, 4HBA, IB-XA, TPO, and Irg184 used in the examples and comparative examples are as follows.

[Chemical 5]

[Evaluation of photocurable composition]

With respect to the photocurable composition obtained in the above Examples and Comparative Examples, the compatibility, the photocurability, the tensile modulus of the cured film, the breaking strength, the elongation at break, and the peeling property were evaluated as follows.

(1) Compatibility

Whether or not each component of the obtained photocurable composition was completely dissolved was visually observed. The evaluation criteria are as follows.

○: Each component was dissolved, and the ink was transparent.

×: Some of the analysis showed that the ink was cloudy.

(2) Photohardenability

A glass substrate of 4 cm square was prepared, and 0.05 g of a photocurable composition was dropped on a glass substrate using a Pasteur pipette, and the glass substrate was laminated. Thereafter, after the h-ray transmission filter was further laminated, ultraviolet rays were irradiated using an ultraviolet irradiation device (TME-400PRC manufactured by Topcon Co., Ltd.). The cumulative exposure amount of the irradiation was measured by an integrated photometer UIT-201 of a photoreceiver UVD-405PD manufactured by a oxtail motor (sand), and the result was 500 mJ/cm ² .

After the ultraviolet ray was irradiated, one of the laminated glass substrates was peeled off, and the surface state of the cured film when the finger touched the surface of the substrate was observed with a microscope. The evaluation criteria are as follows.

○: There was no trace of finger contact on the surface of the cured film.

△: A small amount of finger contact was left on the surface of the cured film.

×: Traces of finger contact were completely left on the surface of the cured film.

(3) tensile modulus, breaking strength, elongation at break

The photocurable composition was dropped on a glass substrate to which an aluminum foil was attached, and spin coating (rotation speed: 300 rpm) was carried out, and this was placed in a replacement tank for an ultraviolet curing device which was replaced with nitrogen. Thereafter, the h-ray transmission filter was laminated, and ultraviolet rays were irradiated using an ultraviolet irradiation device (TME-400PRC manufactured by Topcon Co., Ltd.). The cumulative exposure amount of the irradiation was measured by an integrated photometer UIT-201 equipped with a photoreceptor UVD-405PD manufactured by a oxtail motor (sand), and found to be 500 mJ/cm ² .

After the ultraviolet ray was irradiated, the cured film was peeled off from the aluminum foil to prepare a test piece (5 mm × 25 mm × 30 μm). Then, the tensile properties of the cured film, that is, tensile modulus (MPa), breaking strength (MPa), and elongation at break (%) were determined using EZ Graph (trade name; Shimadzu Corporation). Further, the measurement was performed by setting the distance between the chucks to 15 mm and the stretching speed to 5 mm/min.

The above test was carried out in accordance with ASTM D882.

(4) Peelability of hardened material from PTFE sheet

0.05 g of a photocurable composition was dropped on a glass substrate to which a PTFE sheet was attached, and this was placed in a replacement tank for an ultraviolet curing device which was replaced with nitrogen. Thereafter, the h-ray transmission filter was laminated, and ultraviolet (Ultraviolet, UV) irradiation was performed using an ultraviolet irradiation device (TME-400 PRC manufactured by Topcon Co., Ltd.). The cumulative exposure amount of the irradiation was measured by an integrated photometer UIT-201 equipped with a photoreceptor UVD-405PD manufactured by a oxtail motor (sand), and found to be 500 mJ/cm ² . The cured product formed on the PTFE after irradiation with ultraviolet rays was sandwiched with tweezers, and the peel resistance from the PTFE sheet was investigated. The evaluation criteria are as follows.

◎: The cured product can be peeled off without substantially applying force.

○: When a force is applied to the extent that damage is not caused to the cured product, the cured product is peeled off.

×: The cured product was not peeled off even when a force was applied.

According to the results shown in Table 1, it is understood that the ink of the photocurable composition 1 to the photocurable composition 10 has good compatibility and light hardening.

Further, the cured film of the photocurable composition 1 to the photocurable composition 10 is cured, and the cured film has a tensile modulus of 10 MPa to 500 MPa, a breaking strength of 1 MPa to 50 MPa, and a breaking elongation of 10% to 100%. The value is good. Moreover, the peelability of these hardened materials from a PTFE sheet is also good.

[Industrial availability]

The optically curable composition for optical stereoscopic molding of the present invention is cured by an optical three-dimensional molding method, and the obtained cured product can be used in an organ model in a medical field, a prototype including a part of engineering plastics, and the like. .

1‧‧‧Optical stereolithic photocurable composition

2‧‧‧ Container

3a‧‧‧ mask

4‧‧‧Support

5‧‧‧Light with a wavelength above 400 nm

6a‧‧‧ hardened layer

7‧‧‧Bottom of the container

Claims (7)

An optical photocurable composition for stereoscopic molding comprising a radically polymerizable compound (A) represented by the formula (1) and a photopolymerization initiator which generates a radical by irradiation with light having a wavelength of 400 nm or more (B) ), and a water-insoluble surfactant (C), (In the formula (1), R ¹ is an a-valent organic group containing a structure represented by the formula (2-1) or the formula (2-2) as a partial structure, and R ² is hydrogen or an alkane having 1 to 6 carbon atoms. Base, a is an integer of 2 or more) The elastic modulus of the tensile test of the cured film having a film thickness of 30 μm obtained by irradiating the photocurable composition with light having a wavelength of 400 nm or more is 10 MPa to 500 MPa, and the breaking strength of the cured film is 1 MPa to 50 MPa. The elongation at break of the film is from 10% to 100%. The optical photocuring composition for stereoscopic molding according to the first aspect of the invention, wherein the photopolymerization initiator (B) is selected from the group consisting of an α-aminoalkylphenone and a fluorenylphosphine oxide compound. One or more of the groups formed. The optical photocuring composition for stereoscopic molding according to the first or second aspect of the invention, wherein the water-insoluble surfactant (C) is selected from the group consisting of a fluorine-based surfactant and an anthrone-based interface. One or more of the groups consisting of the agents. The optical photocurable composition for stereoscopic molding according to any one of the first to third aspects of the present invention, further comprising another radical polymerizable compound (D), and the other radical polymerizable compound ( D) having the structure represented by the formula (3), and having a structure different from the radically polymerizable compound (A); (In the formula (3), R ³ is a monovalent organic group having no CH ₂ =CH-CO-, and R ⁴ is hydrogen or an alkyl group having 1 to 6 carbon atoms). The optical photocurable composition for stereoscopic molding according to the fourth aspect of the invention, wherein R ³ of the other radical polymerizable compound (D) is a compound having a structure represented by the formula (4); 9] (In the formula (4), R ⁵ is a divalent organic group which may have a cyclic structure). A method for producing a molded article, comprising the step of irradiating light having a wavelength of 400 nm or more with the photocurable composition according to any one of claims 1 to 5. The manufacturing method according to claim 6, wherein the light having a wavelength of 400 nm or more is irradiated from the lower side or the horizontal direction of the support.