JP2021146657A - Composition for three-dimensional forming, high molecular weight body, three-dimensional formed article, and manufacturing method of three-dimensional formed article - Google Patents

Abstract

To provide a composition for three-dimensional forming capable of acquiring a solidification matter which is excellent in strength and elongation and has touch feeling close to that of an actual organ.SOLUTION: A composition for three-dimensional forming contains monofunctional acrylate monomer and polyfunctional urethane acrylate oligomer, and the total content of the monofunctional acrylate monomer and the polyfunctional urethane acrylate oligomer is equal to 95 mass% or more to the total amount of the composition, and mol fraction of the monofunctional acrylate monomer and the polyfunctional urethane acrylate oligomer (monofunctional acrylate monomer/polyfunctional urethane acrylate oligomer) is 99.9/0.1-99.99/0.01.SELECTED DRAWING: None

Description

The present invention relates to a composition for three-dimensional modeling, a high molecular weight body, a three-dimensional model, and a method for producing the three-dimensional model.

In recent years, new surgical procedures and medical devices such as laparoscopic surgery and endovascular surgery have been created, and minimally invasive surgery, which is expected to improve postoperative recovery and quality of life (QOL) of patients, is rapidly advancing. doing. At the same time, with the rapid progress of medical technology, there are not a few doctors who have no choice but to go to surgery without being able to fully acquire the technology, and the increasing tendency of medical accidents has become a major social problem. ..
In order to solve this, a training system that enables sufficient skill acquisition before surgery is required. Surgical training to train specialists is conducted through the use of laboratory animals, the use of cadaver (human corpse for dissection), and clinical trials in patients.
However, from a social and moral point of view, it is required to reduce the frequency of use of laboratory animals and cabbage. In order to reduce the frequency of use of laboratory animals and cabbage, there is an increasing demand for alternative medical technologies and training systems that improve safety.

To solve such a problem, a three-dimensional modeling model (hereinafter, organ model) of an affected part or a specific part of the body is used. By using the organ model, it is possible to convey a lot of information that cannot be conveyed by computer images by actually touching and seeing the three-dimensional shape as well as the visual sense.
At this time, it is important to bring the tactile sensation of the organ model closer to the biological texture. For example, if you touch an organ model with your hand and tell that there is a difference in flexibility and stretchability depending on the part, and that the hardness is different in the affected part and the healthy part, the effect of medical education and informed consent will be shown. Can be enhanced. At the same time, it is preferable that the surface and internal structure of the organ model can be reproduced. In recent years, a method for producing a complicated and fine three-dimensional model including a rubber-like material and a hydrogel material has been disclosed by using a layered manufacturing method using an inkjet head or the like.

For example, it contains a monofunctional acrylate monomer and a polyfunctional monomer, the molecular weight of the monofunctional acrylate monomer and the glass transition temperature of the homopolymer, the content of the monofunctional acrylate monomer with respect to the total amount of the composition, the monofunctional acrylate monomer and the polyfunctional monomer. An inkjet composition for three-dimensional modeling has been proposed in which a cured product having rubber-like elasticity and elongation and little dimensional change with time can be obtained by adjusting the molar fraction of (for example). See Patent Document 1).
Further, for example, an organ model for practicing a procedure including a hydrogel in which water is contained in a three-dimensional network structure formed by combining a water-soluble organic polymer and a water-swellable layered clay mineral dispersible in water. Has been proposed (see, for example, Patent Document 2).

An object of the present invention is to provide a three-dimensional modeling composition which is excellent in strength and elongation and can obtain a solidified product having a tactile sensation close to that of an actual organ.

The composition for three-dimensional modeling of the present invention as a means for solving the above-mentioned problems contains a monofunctional acrylate monomer and a polyfunctional urethane acrylate oligomer, and contains the monofunctional acrylate monomer and the polyfunctional urethane acrylate oligomer. The total amount is 95% by mass or more with respect to the total amount of the composition, and the molar fraction (monofunctional acrylate monomer / polyfunctional urethane acrylate oligomer) of the monofunctional acrylate monomer and the polyfunctional urethane acrylate oligomer is 99.9. /0.1-99.99 / 0.01.

According to the present invention, it is possible to provide a three-dimensional modeling composition which is excellent in strength and elongation and can obtain a solidified product having a tactile sensation close to that of an actual organ.

(Composition for three-dimensional modeling)
The composition for three-dimensional modeling of the present invention contains a monofunctional acrylate monomer and a polyfunctional urethane acrylate oligomer, and the total content of the monofunctional acrylate monomer and the polyfunctional urethane acrylate oligomer is the total amount of the composition. It is 95% by mass or more, and the molar fraction (monofunctional acrylate monomer / polyfunctional urethane acrylate oligomer) of the monofunctional acrylate monomer and the polyfunctional urethane acrylate oligomer is 99.9 / 0.1-99.99 / 0. It is 0.01, and further contains a polymerization initiator and other components as required.

The present inventors examined the following problems in the conventional technique, and obtained the following findings.
In the prior art, a composition is disclosed in which a cured product having elasticity and elongation like rubber and having no dimensional change with time can be obtained by adjusting the composition of the curable composition. There is a problem that it is not possible to obtain a tactile sensation like that of an actual organ due to the lack of rubber.
Further, in the prior art, it is disclosed that a hydrogel is used to obtain an organ model that is close to the tactile sensation of an actual organ. However, since the hydrogel dries over time, its physical properties must be stored in a closed environment. There is a problem that it changes and is complicated to handle.

By containing the monofunctional acrylate and the polyfunctional acrylate oligomer in a predetermined content, the present inventors are softer than the rubber-like material, and the texture does not change for a long period of time even in a closed environment, and the strength and elongation are maintained. We have found a composition that is excellent in the above and gives a solidified product with a tactile sensation close to that of an actual organ. Since such a composition does not contain water, the obtained solidified product does not contain water, and the physical properties do not change due to drying, so that the handling property is also excellent.

<Monofunctional acrylate monomer>
The "monofunctional acrylate monomer" means an acrylic acid derivative having only one polymerizable functional group in the molecule. Normally, acrylic acid derivatives have a (meth) acryloyl group in the molecule, which functions as a polymerizable functional group. Therefore, a monofunctional acrylate monomer has only one (meth) acryloyl group in the molecule, and other than that. Does not have a polymerizable functional group of. Examples of the acrylic acid derivative include, but are not limited to, a salt of acrylic acid or methacrylic acid, an ester derivative, and the like.

The monofunctional acrylate monomer of the present invention preferably has an ethylene glycol skeleton or a propylene glycol skeleton in the molecule. The ethylene glycol skeleton or the propylene glycol skeleton may form a repeating structure. When the monofunctional acrylate monomer has an ethylene glycol skeleton or a propylene glycol skeleton in the molecule, not only can the toughness and stretchability of the solidified product of the present invention be improved, but it is also important in material jetting discharge. The surface tension can be adjusted.
When the ethylene glycol skeleton or the propylene glycol skeleton forms a repeating structure, the number of repetitions is preferably 3 or less, more preferably 2 or less. When the number of repetitions is 3 or less, it is possible to suppress a decrease in stretchability of the solidified product (cured product) of the composition of the present invention.

The weight average molecular weight of the monofunctional acrylate monomer is preferably 116 or more and less than 237, and more preferably 130 or more and 237 or less. When the weight average molecular weight of the monofunctional acrylate monomer is 116 or more and less than 237, the stretchability of the solidified product (cured product) of the composition of the present invention can be imparted, and the tensile strength can be easily controlled by the amount of oligomer. Become.

The monofunctional acrylate monomer preferably has a hydroxyl group. When the monofunctional acrylate monomer has a hydroxyl group, both the stretchability and the strength of the solidified product (cured product) of the composition of the present invention can be improved.

Examples of the monofunctional acrylate monomer contained in the composition of the present invention include methoxyethyl acrylate, ethoxyethyl acrylate, methoxypropyl acrylate, ethoxypropyl acrylate, methoxydiethylene glycol acrylate, ethoxydiethylene glycol acrylate, methoxydipropylene glycol acrylate, and ethoxydi. Propropylene glycol acrylate, methoxytriethylene glycol acrylate, ethoxytriethylene glycol acrylate, methoxytripropylene glycol acrylate, ethoxytripropylene glycol acrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethylhexyl-diglucol acrylate, tetrahydrofurfuryl Acrylate, Phenoxyethyl Acrylate, Phenoxydiethylene Glycol Acrylate, Phenoxytriethylene Glycol Acrylate, Phenoxypropyl Acrylate, Phenoxydipropylene Glucol Acrylate, Phenoxytripropylene Glycol Acrylate, 2-Hydroxyethyl Acrylate, 2-Hydroxypropyl Acrylate, 2-Hydroxybutyl Examples thereof include acrylate, 4-hydroxybutyl acrylate, and the like, preferably methoxyethyl acrylate, methoxydiethylene glycol acrylate, methoxydipropylene glycol acrylate, methoxytriethylene glycol acrylate, isobutyl acrylate, 2-hydroxyethyl acrylate, and most preferably. , Methoxyethyl acrylate is desirable. These may be used alone or in combination of two or more.

<Polyfunctional urethane acrylate oligomer>
The "polyfunctional urethane acrylate oligomer" means an acrylic acid derivative having two or more polymerizable functional groups in the molecule and further having a plurality of urethane bonds. The polymerizable functional group is typically a (meth) acryloyl group. Therefore, a polyfunctional urethane acrylate oligomer usually has a plurality of (meth) acryloyl groups in the molecule, and the plurality of (meth) acryloyl groups are linked by a structure having a plurality of urethane bonds.

The number of functional groups of the polyfunctional urethane acrylate oligomer is preferably 2 or more and 3 or less, and more preferably 2. When the number of functional groups of the polyfunctional urethane acrylate oligomer is 2 or more and 3 or less, it is possible to suppress a decrease in stretchability of the solidified product (cured product) of the composition of the present invention. The polyfunctional urethane acrylate oligomer may be a mixture of a bifunctional urethane acrylate oligomer and a trifunctional urethane acrylate oligomer, and only the bifunctional urethane acrylate oligomer is more preferable.

The glass transition temperature Tg of the polyfunctional urethane acrylate oligomer is preferably −76 ° C. or higher and 20 ° C. or lower, more preferably −51 ° C. or higher and 12 ° C. or lower, and −40 ° C. or higher and −5 ° C. or lower. More preferably, it is more preferably −40 ° C. or higher and −30 ° C. or lower. When the glass transition temperature Tg of the polyfunctional urethane acrylate oligomer is −76 ° C. or higher and 20 ° C. or lower, it is possible to suppress a decrease in the stretchability of the solidified product (cured product) of the composition of the present invention, and the solidified product The shape can be easily maintained.
The glass transition temperature Tg of the polyfunctional urethane acrylate oligomer can be measured by differential thermal analysis using TG-DTA (manufactured by Rigaku Co., Ltd.).

The weight average molecular weight of the polyfunctional urethane acrylate oligomer is preferably 10,000 or more and 40,000 or less, and more preferably 12,000 or more and 20,000 or less. When the weight average molecular weight of the polyfunctional urethane acrylate oligomer is 10,000 or more, it is possible to prevent the cross-linking points from being too close to each other and becoming difficult to stretch. Further, when the weight average molecular weight of the polyfunctional urethane acrylate oligomer is 40,000 or less, it is possible to suppress the decrease in compatibility with the monofunctional acrylate monomer.
As a method for measuring the weight average molecular weight of the polyfunctional urethane acrylate oligomer, for example, the polyfunctional urethane acrylate oligomer can be obtained and measured by gel permeation chromatography.

Examples of the polyfunctional urethane acrylate oligomer include UV-2000B, 3000B, 3200B, 3300B, 3700B, 6640B (manufactured by Mitsubishi Chemical Corporation); CN9782, CN959, CN9893, CN996, CN9290, CN965, CN964, CN980, CN971, CN9718, etc. Examples thereof include CN978 and CN9004 (manufactured by Sartmer). Among these, UV-3000B, 3300B, 3700B; CN9782 is preferable, and UV-3000B is more preferable.

-Contents of monofunctional acrylate monomer and polyfunctional urethane acrylate oligomer-
The total content of the monofunctional acrylate monomer and the polyfunctional urethane acrylate oligomer is 95% by mass or more, preferably 97.5% by mass or more, and more preferably 99% by mass, based on the total amount of the composition. If the total content of the monofunctional acrylate monomer and the polyfunctional urethane acrylate oligomer is less than 95% by mass with respect to the total amount of the composition, the composition may be difficult to solidify and a desired solidified product may not be obtained. be.

-Mole fraction of monofunctional acrylate monomer and polyfunctional urethane acrylate oligomer-
As for the contents of the monofunctional acrylate monomer and the polyfunctional urethane acrylate oligomer, the molar proportions of the monofunctional acrylate monomer and the polyfunctional urethane acrylate oligomer (monofunctional acrylate monomer / polyfunctional urethane acrylate oligomer) are 99. It is 9 / 0.1-99.99 / 0.01, preferably 99.93 / 0.07 to 99.99 / 0.01, preferably 99.93 / 0.07 to 99.98 / 0.02. More preferred. When the monofunctional acrylate monomer is cured alone, it becomes a viscous liquid and is not suitable for three-dimensional modeling. Therefore, by adding the polyfunctional urethane acrylate oligomer as a cross-linking agent to the monofunctional acrylate monomer, the strength is such that the shape of the solidified product can be maintained while maintaining the stretchability of the solidified product (cured product). It was found that both can be achieved.
At this time, if 0.5 mol% or more of the polyfunctional monomer is added to all the monomers as in Patent Document 1, the amount of the cross-linking component becomes too large, and the stretchability cannot be obtained.
Further, when a cross-linking agent having a small molecular weight is used, cross-linking with a short distance may occur at random positions of the polymer, and since the cross-linking points are fixed, stress concentration is likely to occur and the stretchability is sufficiently exhibited. It may be difficult.
When cross-linking is caused by a small amount of the polyfunctional urethane acrylate oligomer as in the present invention, the chemical cross-linking based on the reaction of the polyfunctional urethane acrylate oligomer and the physical cross-linking caused by the molecular chains of the acrylic polymer and the urethane acrylate cause the cross-linking. A cured product with high toughness can be obtained. Further, when the polyfunctional urethane acrylate oligomer having a specific molecular weight is used, stress concentration is less likely to occur because the distance between the cross-linking points is long, and the stretchability can be further improved.

<Polymerization initiator>
The polymerization initiator is not particularly limited as long as it can promote radical polymerization, and can be appropriately selected depending on the intended purpose. Examples thereof include a photopolymerization initiator and a thermal polymerization initiator.

<< Photopolymerization Initiator >>
As the photopolymerization initiator, any substance that generates radicals by irradiation with light (particularly ultraviolet rays having a wavelength of 220 nm to 400 nm) can be used.
Examples of the photopolymerization initiator include acetophenone, 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, benzophenone, 2-chlorobenzophenone, p, p'-dichlorobenzophenone, p, p-bisdiethylaminobenzophenone and Michler ketone. , Phenyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-propyl ether, benzoin isobutyl ether, benzoin-n-butyl ether, benzyl methyl ketal, thioxanthone, 2-chlorothioxanthone, 2-hydroxy-2 -Methyl-1-phenyl-1-one, 1- (4-isopropylphenyl) 2-hydroxy-2-methylpropan-1-one, methylbenzoylformate, 1-hydroxycyclohexylphenylketone (ig184), azobis Examples thereof include isobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide and the like. These may be used alone or in combination of two or more.

<< Thermal Polymerization Initiator >>
The thermal polymerization initiator is not particularly limited and may be appropriately selected depending on the intended purpose. For example, an azo-based initiator, a peroxide initiator, a persulfate initiator, and a redox (oxidation-reduction) initiator. And so on.
Examples of the azo-based initiator include VA-044, VA-46B, V-50, VA-057, VA-061, VA-067, VA-086, 2,2'-azobis (4-methoxy-2). , 4-Dimethylvaleronitrile) (VAZO 33), 2,2'-azobis (2-amidinopropane) dihydrochloride (VAZO 50), 2,2'-azobis (2,4-dimethylvaleronitrile) (VAZO 52) ), 2,2'-Azobis (isobutyronitrile) (VAZO 64), 2,2'-azobis-2-methylbutyronitrile (VAZO 67), 1,1-azobis (1-cyclohexanecarbonitrile) ( VAZO 88) (above, manufactured by DuPont Chemical), 2,2'-azobis (2-cyclopropylpropionitrile), 2,2'-azobis (methylisobutyrate) (V-601) (above, Wako Pure Chemicals) (Manufactured by Kogyo Co., Ltd.) and the like.
Examples of the peroxide initiator include benzoyl peroxide, acetyl peroxide, lauroyl peroxide, decanoyl peroxide, disetylperoxydicarbonate, and di (4-t-butylcyclohexyl) peroxydicarbonate (trade name). : Perkadox 16S, manufactured by Akzo Nobel), di (2-ethylhexyl) peroxydicarbonate, t-butylperoxypivalate (trade name: Lupersol 11, manufactured by Elf Atchem), t-butylperoxy-2-ethyl Hexanoate (trade name: Trigonox 21-C50, manufactured by Akzo Nobel), dicumyl peroxide and the like can be mentioned.
Examples of the persulfate initiator include potassium persulfate, sodium persulfate, ammonium persulfate and the like.
Examples of the redox (oxidation-reduction) initiator include a combination of a persulfate initiator and a reducing agent such as sodium metahydrosulfate and sodium hydrogen sulfite, and a system based on an organic peroxide and a tertiary amine ( For example, a system based on benzoyl peroxide and dimethylaniline), a system based on an organic hydroperoxide and a transition metal (for example, a system based on cumenehydroperoxide and cobalt naphthate) and the like can be mentioned. These may be used alone or in combination of two or more.

The content of the polymerization initiator is preferably 5% by mass or less, more preferably 1% by mass or more and 3% by mass or less, based on the total amount of the composition.

<Other ingredients>
The other components are not particularly limited as long as the total content of the monofunctional acrylate monomer and the polyfunctional urethane acrylate oligomer is 95% by mass or more with respect to the total amount of the composition, and are appropriately selected depending on the intended purpose. can do. For example, colorants and solvents are added to control the appearance and feel, surfactants, viscosity modifiers and lubricants are added to stabilize the molding, and the properties of the composition and solidified product (cured product). In order to maintain the above for a long period of time, a polymerization inhibitor, an ultraviolet absorber, or the like may be added.

<< Colorant >>
As the colorant, for example, various pigments and dyes that impart black, white, magenta, cyan, yellow, green, orange, glossy colors such as gold and silver, and the like can be used.
As the pigment, an inorganic pigment or an organic pigment can be used, and one type may be used alone or two or more types may be used in combination.
As the inorganic pigment, for example, carbon black (CI pigment black 7) such as furnace black, lamp black, acetylene black, and channel black, iron oxide, and titanium oxide can be used.
Examples of the organic pigment include azo pigments such as insoluble azo pigments, condensed azo pigments, azolakes and chelate azo pigments, phthalocyanine pigments, perylene and perinone pigments, anthraquinone pigments, quinacridone pigments, dioxane pigments, thioindigo pigments and isoindolinone pigments. Polycyclic pigments such as quinophthalone pigments, dye chelate (for example, basic dye type chelate, acidic dye type chelate, etc.), dyeing lake (for example, basic dye type lake, acidic dye type lake, etc.), nitro pigment, nitroso pigment , Aniline black, daylight fluorescent pigments and the like.
Further, in order to improve the dispersibility of the pigment, a dispersant may be further contained. The dispersant is not particularly limited, and examples thereof include dispersants commonly used for preparing pigment dispersions such as polymer dispersants.
As the dye, for example, an acid dye, a direct dye, a reactive dye, and a basic dye can be used, and one type may be used alone or two or more types may be used in combination.
When used in the material jetting method, it may be appropriately determined in consideration of dispersibility in the energy ray-curable liquid, and is preferably 0.1% by mass or more and 5% by mass or less with respect to the total amount of the precursor. ..
The means and conditions for preparing the material in the composition are not particularly limited, but for example, unsaturated acid monomers, metal salts, polymerizable monomers, and other components are added to ball mills, kitty mills, disc mills, pin mills, dyno mills, and the like. It can be prepared by putting it in the disperser of the above and mixing it with the above composition.

<< Viscosity modifier >>
Examples of the viscosity modifier include acrylic resin, butyral resin, ethylene-vinyl acetate copolymer, polyvinyl alcohol and the like.
<< Lubricant >>
Examples of the lubricant include polyester resin, polyvinyl acetate resin, silicone resin, kumaron resin, fatty acid ester, glyceride, and wax.
<< Polymerization inhibitor >>
Examples of the polymerization inhibitor include phenol compounds [hydroquinone, hydroquinone monomethyl ether, 2,6-di-t-butyl-p-cresol, 2,2-methylene-bis- (4-methyl-6-t-butylphenol). ), 1,1,3-Tris- (2-methyl-4-hydroxy-5-t-butylphenyl) butane, etc.], sulfur compounds [dilaurylthiodipropionate, etc.], phosphorus compounds [triphenylphosphite, etc.] ], Amine compounds [phenothiazine, etc.] and the like. These may be used alone or in combination of two or more.
The content of the polymerization inhibitor is preferably 5% by mass or less based on the total amount of the composition, and more preferably 0.1% by mass or more and 5% by mass or less from the viewpoint of the stability of the monomer and the polymerization rate.

(High molecular weight body)
The high molecular weight body of the present invention is obtained by solidifying the three-dimensional modeling composition of the present invention.
The high molecular weight compound of the present invention contains a polymer of a monofunctional acrylate monomer and a polyfunctional urethane acrylate oligomer contained in the composition for three-dimensional modeling of the present invention.
The high molecular weight material of the present invention preferably has a tensile stress at the time of 400% strain of 0.02 MPa or more and 0.6 MPa or less, and preferably 0.02 MPa or more and 0.2 MPa or less. When the tensile stress at the time of 400% strain is 0.02 MPa or more and 0.6 MPa or less, an organ model close to the biological texture can be obtained.
The method for measuring the tensile stress at the time of 400% strain is measured by using the following method.

[Tensile stress at 400% strain]
-Preparation of tensile evaluation test piece-
A 4 mm thick silicone resin (made by Togawa Rubber) was punched with a tensile No. 6 dumbbell-shaped test piece punching blade (JIS K 6251 compliant, Polymer Instruments Co., Ltd.), and a No. 6 dumbbell-shaped hole was opened. Obtain a silicone sheet.
The obtained silicone sheet was placed on a soda-lime glass plate (GB300, manufactured by AS ONE), 1.0 g of the three-dimensional modeling composition was poured into the No. 6 dumbbell-shaped hole, and an ultraviolet irradiator (device name: SPOT CURE SP5) was poured. -250DB, manufactured by Ushio, Inc.) is irradiated with a light amount of 350 mJ / cm2 to solidify (cure) the three-dimensional modeling composition.
The step of pouring the three-dimensional modeling composition into the hole and the step of curing by ultraviolet irradiation are repeated until the No. 6 dumbbell-shaped hole is filled with the solidified product (cured product).
The silicone sheet is removed, and the solidified product (cured product) and the glass plate are separated to obtain a tensile evaluation test piece.
-Tensile test evaluation-
A digital force gauge (ZTS-50N, manufactured by Imada Co., Ltd.) is attached to a vertical electric measuring stand (EMX-1000N, manufactured by Imada Co., Ltd.), and both ends of the tensile evaluation test piece are film chucks (FC-41U, manufactured by Imada Co., Ltd.). ), And a tensile test is performed at a speed of 100 mm / min. Other tensile test conditions conform to JIS K 6251: 2017. As for the tensile evaluation test pieces to be used, only those having no cracks or voids are used for the tensile evaluation in the above-mentioned preparation. The average value of the evaluation by 5 test pieces is used as the evaluation.

(Three-dimensional model)
The three-dimensional model of the present invention is formed by a flexible material obtained by solidifying the three-dimensional model composition of the present invention.
The use of the three-dimensional model of the present invention is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it can be suitably used exclusively as an organ model.
In the three-dimensional model of the present invention, the tensile stress at the time of 400% strain is preferably 0.02 MPa or more and 0.6 MPa or less, and preferably 0.02 MPa or more and 0.2 MPa or less. When the tensile stress at the time of 400% strain is 0.02 MPa or more and 0.6 MPa or less, an organ model close to the biological texture can be obtained. That is, the tactile sensation and texture given by the organ model are similar to the sensation of being pushed back from the actual organ. This is because the organ model is often a rigid body, so the sensation of holding the organ model or pushing it with a finger, that is, the repulsive force applied when it is compressed, is linked to the "texture of the organ model". .. On the other hand, when the procedure training is performed using the organ model, steps such as incision, peeling, and suturing (ligation) of the organ model are involved. At this time, the texture given by the organ model is similar to the feeling of pulling the organ model. This is dominated by the sensation of pinching the organ model in the above steps and pulling the site together for suturing. Since the organ model in the present invention is assumed to be used for procedure training, it is important to control the tensile strength. That is, it is unnatural as a living body unless it is stretched by at least 400% or more. Therefore, when it is used as an organ model, it is required to stretch by 400% or more, and the tensile strength when it is further stretched by 400% or more is the actual organ. It was found by the present inventors that the closer it is to the feel of, the more suitable it is as an organ model for procedure training. At the time of 400% elongation, if the tensile stress is less than 0.02 MPa, it is softer than fat, so it has almost no use as an organ model, and if it exceeds 0.6 MPa, there are only a limited number of cases as a flexible organ. Further, if it falls within the range of 0.02 MPa or more and 0.2 MPa or less, it can be pulled by using forceps or the like, so that the range of application as an organ model can be widened.

(Manufacturing method of three-dimensional model)
The method for producing a three-dimensional model of the present invention contains a monofunctional acrylate monomer and a polyfunctional urethane acrylate oligomer, and the content of the monofunctional acrylate monomer and the polyfunctional urethane acrylate oligomer is relative to the total amount of the composition. It is 95% by mass or more, and the molar fraction (monofunctional acrylate monomer / polyfunctional urethane acrylate oligomer) of the monofunctional acrylate monomer and the polyfunctional urethane acrylate oligomer is 99.9 / 0.1-99.99 / 0. It includes a solidification step of solidifying the three-dimensional modeling composition of 0.01, and further includes other steps accordingly.
That is, the method for producing a three-dimensional model of the present invention includes a solidification step of solidifying the three-dimensional model composition of the present invention.

<solidification process>
The solidification step is not particularly limited as long as the three-dimensional modeling composition can be solidified, and can be appropriately selected depending on the intended purpose. For example, a block (solidification, curing) of the three-dimensional modeling composition can be selected. A method of generating an object) and cutting it into an arbitrary shape, a method of thermally melting a solidified product of the three-dimensional modeling composition to form a cast, and a method of encapsulating the three-dimensional modeling composition in a mold to solidify it. There are a method, a method of laminating molding using the three-dimensional modeling composition, and the like.

<< Method of encapsulating a three-dimensional modeling composition in a mold and solidifying it >>
When molding using a mold, it is preferable to enclose the three-dimensional molding composition in a mold having a desired shape and solidify (cure) the composition. In the method of hot-melting the solidified product of the three-dimensional modeling composition and pouring it into a mold, there is a concern that the viscosity of the melt is high and the initial texture changes due to heat.
The mold molding method using the three-dimensional molding composition is a mold molding step of molding a mold for manufacturing a three-dimensional model using a cutting device, a three-dimensional printer, or the like based on three-dimensional data of the three-dimensional model. And the molding step of pouring the composition for three-dimensional molding into this mold and curing it to form the mold.

The three-dimensional printer used in the mold molding process is not particularly limited in method, but since the three-dimensional modeling composition is injected and cured, there is no leakage of the three-dimensional modeling composition. It is preferable that the method uses a material or method.
Specifically, fused deposition modeling (FDM), stereolithography (stereolithography), inkjet methods such as material jetting and binder jetting, powder sintering lamination modeling (SLS / SLM), and the like are preferable. The Fused Deposition Modeling Method (FDM) is a method of heating a material containing a thermoplastic resin to form a softened product, and extruding the material to form a three-dimensional model as a laminated body.

Further, as a means used in a process of forming a mold other than a three-dimensional printer, for example, a means by cutting such as a cutting RP machine, an NC lathe, an impression material, or mechanical polishing is preferable. Among these, the Fused Deposition Modeling (FDM) and the cutting RP machine are preferable as the means used in the process of molding the mold.
When the mold is manufactured by the thermal melting lamination method (FDM) or the cutting RP machine, the three-dimensional data used when manufacturing the three-dimensional model does not need to perform special data processing for forming the staircase structure. This is because the staircase structure may be formed from the accumulation traces of the thermal melting lamination method (FDM) itself or the cutting traces by the cutting RP machine, and the steps in the staircase structure may be substantially evenly spaced.

Next, the three-dimensional molding composition is poured into the molded mold and cured. For example, a male mold (core) mold and a female mold (cavity) mold are combined, and the three-dimensional modeling composition is poured into a gap formed between the two and cured.
When curing with a thermal polymerization initiator, the reaction temperature is controlled according to the type of initiator. The composition for three-dimensional modeling is injected, sealed to block air (oxygen), and then heated to room temperature or a predetermined temperature to allow the polymerization reaction to proceed. After the polymerization is completed, it is taken out from the mold to form a three-dimensional model.
When curing with a photopolymerization initiator, it is necessary to irradiate the precursor with energy rays such as ultraviolet rays as a curing means. Therefore, the mold used is made of a material that is transparent to the energy rays. After injecting into such a mold and sealing it to block air (oxygen), energy rays are irradiated from the outside of the mold. After the polymerization is completed in this way, a three-dimensional model is formed by removing it from the mold.

<< Method of Laminated Modeling Using Composition for Three-dimensional Modeling >>
In the case of laminating modeling using the three-dimensional modeling composition, a method is used in which the three-dimensional modeling composition is irradiated with active energy rays and radically polymerized to form a film, and the three-dimensional modeling composition is laminated to obtain a three-dimensional model. Especially preferable. Examples of such a method include stereolithography (hereinafter, SLA method) and material jetting method (hereinafter, MJ method).

[SLA method]
The SLA method is characterized in that by exposing the three-dimensional modeling composition layer by layer, the composition is sequentially cured and laminated to form a three-dimensional modeling object.
Each layer of this laminated body is obtained by irradiating the liquid surface of the three-dimensional modeling composition with light. The liquid level can be leveled with a recorder or the like. At this time, by selectively irradiating with light, a solidified product (cross-section cured layer) having a cross section of a desired pattern can be obtained.
The method for producing a three-dimensional model is to irradiate the three-dimensional modeling composition with light to form a solidified product (cross-section cured layer) of the three-dimensional modeled composition, and to form the solidified product (cross-section cured layer) on the solidified product (cross-section cured layer). , The three-dimensional modeling composition is supplied again and irradiated with light to further form a solidified product (cross-sectional cured layer) of the three-dimensional modeling composition, and thereafter, by repeating this, a plurality of solidified products ( A three-dimensional model formed by laminating (cross-section cured layers) and integrating them is obtained.

The means for selectively irradiating the three-dimensional modeling composition with light is not particularly limited, and various means can be adopted.
For example, (a) a means for irradiating the composition while scanning a laser beam or a convergent light obtained by using a lens, a mirror, or the like, and (b) a mask having a light transmitting portion having a predetermined pattern are used. A means for irradiating the composition with non-convergent light via a mask, (c) a light guide member formed by bundling a large number of optical fibers is used, and light is composed via an optical fiber corresponding to a predetermined pattern in the light guide member. A means for irradiating an object, (d) a means for repeatedly performing batch exposure for each fixed area, and the like can be adopted.
Further, in the means using the mask of (b) above, as a mask, a mask image composed of a light transmitting region and a light opaque region is electro-optically formed according to a predetermined pattern by the same principle as that of a liquid crystal display device. It is also possible to use the one that does.
When the target three-dimensional model has fine parts or requires high dimensional accuracy, the spot diameter is used as a means for selectively irradiating the three-dimensional structure composition with light. It is preferable to employ means for scanning a small laser beam.
When the three-dimensional modeling composition is contained in the container, the light irradiation surface (for example, the scanning plane of the convergent light) is the liquid surface of the composition and the contact surface with the vessel wall of the translucent container. It may be any of. When the liquid surface of the three-dimensional modeling composition or the contact surface with the vessel wall is used as the light irradiation surface, light can be irradiated directly from the outside of the container or through the vessel wall.
As described above, the three-dimensional model of the present invention can be produced by an optical three-dimensional modeling method such as an additive manufacturing method.
In the optical three-dimensional modeling method, usually, after curing a specific portion of the three-dimensional modeling composition, the light irradiation position (irradiation surface) is continuously or stepwise from the cured portion to the uncured portion. By moving, the cured portions are laminated to form a desired three-dimensional shape.
Here, the irradiation position can be moved by various methods, for example, any one of the light source, the storage container of the composition, and the cured portion of the composition can be moved, or the composition is additionally supplied to the storage container. There are methods such as doing.
A commercially available stereolithography modeling machine may be used. Examples of a commercially available stereolithography modeling machine include Form2 (manufactured by Formlab) and the like.

[MJ method]
The MJ method includes repeating a first step of forming a film with the three-dimensional modeling composition and a second step of solidifying the film formed in the first step a plurality of times, and the film. (Layer) is laminated to form a modeled object, and if necessary, other steps are included.
In addition, the MJ method includes the first step of forming a film with the three-dimensional modeling composition and
The third step of forming the film by the curable support composition containing the curable support material at a position different from the position where the film by the three-dimensional modeling composition was formed, and the first step and the third step. The fourth step of solidifying the film formed in the step is repeated a plurality of times, and the film (layer) is laminated to form a modeled product, and further includes other steps as necessary.

The curable support material is a composition different from the three-dimensional modeling composition, and is not particularly limited as long as it is a conventionally used support material material, and can be appropriately selected depending on the intended purpose. For example, those described in Japanese Patent Application Laid-Open No. 2019-151097 can be mentioned.

In the MJ method, by increasing the number of heads, colored ink and other radically polymerized materials can be molded at the same time, so that it can be used for color molding and hybrid molding with other members.
The number of repetitions varies depending on the size, shape, structure, etc. of the three-dimensional model to be produced and cannot be unconditionally specified, but if the thickness per layer is in the range of 10 μm to 50 μm, it can be peeled off with high accuracy. Since it is possible to model without any problem, it is preferable to repeatedly stack the three-dimensional model to be produced by the height of the model.
The step of forming a film is a step of forming a film with the three-dimensional modeling composition, and is carried out by means for forming the film. If a liquid other than the three-dimensional modeling composition can be applied at the time of film formation, a liquid in which the amount of the three-dimensional modeling composition added is changed (including the case where no additive is not added) may be applied. can.
The means for forming the film is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a dispenser method, a spray method, and an inkjet method. A known device can be preferably used to carry out these methods.
Among these, the dispenser method is excellent in quantification of droplets, but the coating area is narrow, and the spray method can easily form fine ejected substances, has a wide coating area, and is excellent in coating property. The quantification of droplets is poor, and scattering occurs due to the spray flow. Therefore, in the present invention, the inkjet method is particularly preferable. The inkjet method has an advantage that the quantification of droplets is better than that of the spray method and a large coating area can be obtained as compared with the dispenser method, and is preferable in that a complicated three-dimensional shape can be formed accurately and efficiently. ..
A commercially available inkjet stereolithography machine may be used. Examples of commercially available inkjet devices include Azilista (manufactured by KEYENCE CORPORATION) and the like.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

(Example 1)
-Preparation of composition 1 for three-dimensional modeling-
2-Hydroxyethyl acrylate (manufactured by Tokyo Kasei Kogyo Co., Ltd., molecular weight: 116.05) 99.5 parts by mass as monofunctional acrylate monomer, UV-6640B (weight average molecular weight: 5000, glass transition of oligomer alone) as polyfunctional urethane acrylate oligomer Temperature: 12 ° C., Number of acrylic functional groups: 2, manufactured by Mitsubishi Chemical) 0.5 parts by mass, and 1-hydroxycyclohexylphenyl ketone (Omnirad 184, manufactured by IGM Resins BV) as a photopolymerization initiator was added by 2 parts by mass. The mixture was stirred for 24 hours to obtain a three-dimensional modeling composition 1.
After stirring, confirm that the oligomer and initiator are dissolved in the monomer. The total of the monofunctional acrylate monomer and the polyfunctional urethane acrylate oligomer is 98% by mass of the total weight, and the molar ratio of the monofunctional acrylate monomer and the polyfunctional urethane acrylate oligomer (monofunctional acrylate monomer / polyfunctional urethane acrylate oligomer). Is 99.988 / 0.012.

-Preparation of tensile evaluation test piece-
A 4 mm thick silicone resin (made by Togawa Rubber) was punched with a tensile No. 6 dumbbell-shaped test piece punching blade (JIS K 6251 compliant, Polymer Instruments Co., Ltd.), and a No. 6 dumbbell-shaped hole was opened. Obtain a silicone sheet.
The obtained silicone sheet was placed on a soda-lime glass plate (GB300, manufactured by AS ONE), 1.0 g of the three-dimensional modeling composition 1 was poured into a No. 6 dumbbell-shaped hole, and an ultraviolet irradiator (device name: SPOT CURE) was used. The composition for three-dimensional modeling was solidified (cured) by irradiating with a light amount of 350 mJ / cm2 with SP5-250DB (manufactured by Ushio, Inc.).
The step of pouring the three-dimensional modeling composition 1 into the hole and the step of curing by ultraviolet irradiation were repeated until the No. 6 dumbbell-shaped hole was filled with the solidified product (cured product).
The silicone sheet was removed, and the solidified product (cured product) and the glass plate were separated to obtain a tensile evaluation test piece 1.
The tensile evaluation test piece 1 is a high molecular weight body obtained by solidifying (curing) the three-dimensional modeling composition 1.

(Examples 2 to 12 and Comparative Examples 1 to 6)
In Example 1, tensile evaluation test pieces 2 to 18 were obtained in the same manner as in Example 1 except that the composition was changed to that shown in Table 1. However, in Examples 10 and 11, the modeling method was changed to the method described below.

In Example 10, laminated modeling was performed by a stereolithography method (SLA).
-Laminate modeling by stereolithography method-
Modeling was performed using Form2 (manufactured by Formlab Co., Ltd.) as a commercially available 3D printer by a stereolithography method. The three-dimensional modeling composition 3 obtained in Example 3 was placed in a resin tank, and modeling was performed in the open mode. As for the shape, a tensile evaluation test piece / blood vessel / tumor model (Φ10 mm) was output, respectively, and a tensile evaluation test piece 10, a blood vessel model 10, and a tumor model 10 were obtained. A tensile evaluation test piece 10 was used for the tensile evaluation test, and a blood vessel model 10 and a tumor model 10 were used for expert evaluation.

In Example 11, laminated modeling was performed by the material jetting method (MJ).
-Laminate modeling by material jetting method-
The three-dimensional modeling composition 3 obtained in Example 3 was used as a model agent in Agilista3000 (manufactured by KEYENCE Co., Ltd.) as a 3D printer by the material jetting method, and the tensile evaluation test piece / blood vessel / A tumor model (Φ10 mm) was output, respectively, and a tensile evaluation test piece 11 and a blood vessel model 11 and a tumor model 11 were obtained. The tensile evaluation test piece 11 was used for the tensile evaluation test, and the blood vessel model 11 and the tumor model 11 were used for the expert evaluation.

Details of the materials used in the examples and comparative examples are as follows.
(Monofunctional acrylate monomer)
2-Hydroxyethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd., weight average molecular weight: 116.05, HEA)
-Methoxydipropyl acrylate (manufactured by Sigma-Aldrich, weight average molecular weight: 260.13, AMP200)
-Phenoxydiethylene glycol acrylate (manufactured by Kyoeisha Chemical Co., Ltd., weight average molecular weight: 236.26, P2HA)
-Methoxydipropylene glycol acrylate (manufactured by Kyoeisha Chemical Co., Ltd., weight average molecular weight: 2021, DPM-A)
-Methoxytriethylene glucol acrylate (manufactured by Kyoeisha Chemical Co., Ltd., weight average molecular weight: 176.07, MTG-A)
-Methoxyethyl acrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., weight average molecular weight: 130.06, 2-MTA)
(Polyfunctional urethane acrylate oligomer)
-UV-6640B (Weight average molecular weight: 5,000, glass transition temperature of oligomer alone: 12 ° C, number of acrylic functional groups: 2, manufactured by Mitsubishi Chemical Corporation)
-UV-3300B (Weight average molecular weight: 13,000, glass transition temperature of oligomer alone: -30 ° C, number of acrylic functional groups of oligomer: 2, manufactured by Mitsubishi Chemical Corporation)
-UV-3700B (Weight average molecular weight: 38,000, glass transition temperature of oligomer alone: -6 ° C, number of acrylic functional groups: 2, manufactured by Mitsubishi Chemical Corporation)
-UV-3000B (weight average molecular weight: 18,000, glass transition temperature of oligomer alone: -39 ° C, number of acrylic functional groups: 2, manufactured by Mitsubishi Chemical Corporation)
CN973 (weight average molecular weight: 6,000, glass transition temperature of oligomer alone: -51 ° C, number of acrylic functional groups: 2, manufactured by Arkema Co., Ltd.)
(Photopolymerization initiator)
1-Hydroxycyclohexylphenyl ketone (Omnirad 184, manufactured by IGM Resins BV)

Next, the obtained tensile evaluation test pieces 1 to 18 were subjected to "tensile test evaluation" and "expert evaluation" as follows. The results are shown in Table 3.

<Tensile test evaluation>
A digital force gauge (ZTS-50N, manufactured by Imada Co., Ltd.) is attached to a vertical electric measuring stand (EMX-1000N, manufactured by Imada Co., Ltd.), and both ends of the tensile evaluation test piece are film chucks (FC-41U, manufactured by Imada Co., Ltd.). ), And a tensile test was performed at a speed of 100 mm / min. Other tensile test conditions conform to JIS K 6251: 2017. As for the tensile evaluation test pieces used, only those having no cracks or voids were used for the tensile evaluation in the above-mentioned preparation. The average value of the evaluation by 5 test pieces was used as the evaluation.

<Expert evaluation>
Three doctors with 8 to 15 years of work experience at the medical office pulled the tensile evaluation test piece and sensory evaluated the tactile sensation.

In the examples, it was possible to obtain a tensile strength close to that of an actual organ. In addition, the elongation at break was 400% or more. Further, in the expert evaluation, the hardness of the test piece of Example 1 was close to the upper limit, and the elongation was sufficiently obtained. It was evaluated that it can be used as a material for organ models. The test piece of Example 2 was evaluated to be usable as a material for an organ model, although it was hard but within the permissible range, and it was difficult to extend it below this. The test piece of Example 3 was evaluated to be soft, sufficiently stretchable, and usable as a material for an organ model. The test piece of Example 4 was evaluated to be soft, but it was difficult to extend it below this, but it could be used as a material for an organ model. The test piece of Example 5 was evaluated to be soft, but it was difficult to extend it below this, but it could be used as a material for an organ model. The test piece of Example 6 was evaluated as being soft and sufficiently stretchable, and could be used as a material for an organ model. The test piece of Example 7 was evaluated as having softness and sufficient elongation, and could be used as a material for an organ model. The test piece of Example 8 was evaluated as having softness and sufficient elongation, and could be used as a material for an organ model. The test piece of Example 9 was evaluated to be soft, but it was difficult to extend it below this, but it could be used as a material for an organ model. The test piece of Example 10 was evaluated as being close to the softest organ (fat, etc.) in terms of organ softness, having sufficient elongation, and being usable as a material for an organ model. The test piece of Example 11 was evaluated as having softness and sufficient elongation, and could be used as a material for an organ model. The test piece of Example 12 was evaluated as being soft and sufficiently stretchable, and could be used as a material for an organ model.
On the other hand, in the comparative example, suitable ones were not obtained in terms of both tensile strength and elongation at break. Also, in the expert evaluation, the test piece of Comparative Example 1 was evaluated as not suitable as a material for an organ model because it is hard and does not stretch sufficiently. The test piece of Comparative Example 2 was evaluated as not suitable as a material for an organ model because its hardness was moderate but its elongation was insufficient. No test piece could be obtained for Comparative Example 3. The test piece of Comparative Example 4 was evaluated as not suitable as a material for an organ model because it was considered that the test piece was too soft and there was no corresponding organ. The test piece of Comparative Example 5 was evaluated as being too hard to be suitable as a material for an organ model. The test piece of Comparative Example 6 was evaluated as not suitable as a material for an organ model because it was hard and did not stretch sufficiently.

Examples of aspects of the present invention are as follows.
<1> With a monofunctional acrylate monomer
The total content of the monofunctional acrylate monomer and the polyfunctional urethane acrylate oligomer containing the polyfunctional urethane acrylate oligomer is 95% by mass or more based on the total amount of the composition.
The mole fraction (monofunctional acrylate monomer / polyfunctional urethane acrylate oligomer) of the monofunctional acrylate monomer and the polyfunctional urethane acrylate oligomer is 99.9 / 0.1-99.99 / 0.01. It is a characteristic composition for three-dimensional modeling.
<2> The composition for three-dimensional modeling according to <1>, wherein the monofunctional acrylate monomer has an ethylene glycol skeleton or a propylene glycol skeleton.
<3> The polyfunctional urethane acrylate oligomer has a number of functional groups of 2 or more and 3 or less, and a glass transition temperature Tg of −51 ° C. or more and 12 ° C. or less. The three-dimensional modeling composition described.
<4> The composition for three-dimensional modeling according to any one of <1> to <3>, wherein the polyfunctional urethane acrylate oligomer has a weight average molecular weight of 10,000 or more and 40,000 or less.
<5> The composition for three-dimensional modeling according to any one of <1> to <4>, which further contains a polymerization initiator.
<6> A high molecular weight body characterized by being obtained by solidifying the three-dimensional modeling composition according to any one of <1> to <5>.
<7> The high molecular weight body according to <6>, wherein the tensile stress at the time of 400% strain is 0.02 MPa or more and 0.2 MPa or less.
<8> A three-dimensional model obtained by solidifying the composition for three-dimensional modeling according to any one of <1> to <5>.
<9> The three-dimensional model according to <8>, which is an organ model.
<10> With a monofunctional acrylate monomer
Contains polyfunctional urethane acrylate oligomers,
The content of the monofunctional acrylate monomer and the polyfunctional urethane acrylate oligomer is 95% by mass or more based on the total amount of the composition.
For three-dimensional modeling in which the mole fraction (monofunctional acrylate monomer / polyfunctional urethane acrylate oligomer) of the monofunctional acrylate monomer and the polyfunctional urethane acrylate oligomer is 99.9 / 0.1-99.99 / 0.01. It is a method for producing a three-dimensional molded product, which comprises a solidification step of solidifying the composition.
<11> The method for producing a three-dimensional model according to <10>, wherein the solidification step includes encapsulating the three-dimensional modeling composition in a mold having a desired shape and solidifying the composition.
<12> The solidification step is
The first step of forming a film with the three-dimensional modeling composition and
The second step of solidifying the film formed in the first step and
The method for producing a three-dimensional model according to <10>, which comprises repeating the above-mentioned <10> a plurality of times.
<13> The solidification step is
The first step of forming a film with the three-dimensional modeling composition and
The third step of forming the film by the curable support composition containing the curable support material at a position different from the position where the film by the three-dimensional modeling composition was formed, and
The fourth step of solidifying the film formed in the first step and the third step, and
The method for producing a three-dimensional model according to <10>, which comprises repeating the above-mentioned <10> a plurality of times.

The composition for three-dimensional modeling according to any one of <1> to <5>, the high molecular weight substance according to any one of <6> to <7>, or any of the above <8> to <9>. The three-dimensional model described and the method for producing a three-dimensional model according to any one of <10> to <13> can solve the conventional problems and achieve the object of the present invention.

Japanese Unexamined Patent Publication No. 2015-07825 Japanese Unexamined Patent Publication No. 2015-138192

Claims (13)

With a monofunctional acrylate monomer
The total content of the monofunctional acrylate monomer and the polyfunctional urethane acrylate oligomer containing the polyfunctional urethane acrylate oligomer is 95% by mass or more based on the total amount of the composition.
The mole fraction (monofunctional acrylate monomer / polyfunctional urethane acrylate oligomer) of the monofunctional acrylate monomer and the polyfunctional urethane acrylate oligomer is 99.9 / 0.1-99.99 / 0.01. A characteristic composition for three-dimensional modeling. The composition for three-dimensional modeling according to claim 1, wherein the monofunctional acrylate monomer has an ethylene glycol skeleton or a propylene glycol skeleton. The three-dimensional modeling composition according to any one of claims 1 to 2, wherein the polyfunctional urethane acrylate oligomer has 2 or more and 3 or less functional groups and a glass transition temperature Tg of −51 ° C. or more and 12 ° C. or less. .. The composition for three-dimensional modeling according to any one of claims 1 to 3, wherein the polyfunctional urethane acrylate oligomer has a weight average molecular weight of 10,000 or more and 40,000 or less. The composition for three-dimensional modeling according to any one of claims 1 to 4, further containing a polymerization initiator. A high molecular weight body obtained by solidifying the three-dimensional modeling composition according to any one of claims 1 to 5. The high molecular weight body according to claim 6, wherein the tensile stress at the time of 400% strain is 0.02 MPa or more and 0.2 MPa or less. A three-dimensional model obtained by solidifying the composition for three-dimensional modeling according to any one of claims 1 to 5. The three-dimensional model according to claim 8, which is an organ model. With a monofunctional acrylate monomer
Contains polyfunctional urethane acrylate oligomers,
The content of the monofunctional acrylate monomer and the polyfunctional urethane acrylate oligomer is 95% by mass or more based on the total amount of the composition.
For three-dimensional modeling in which the mole fraction (monofunctional acrylate monomer / polyfunctional urethane acrylate oligomer) of the monofunctional acrylate monomer and the polyfunctional urethane acrylate oligomer is 99.9 / 0.1-99.99 / 0.01. A method for producing a three-dimensional molded product, which comprises a solidification step of solidifying the composition. The method for producing a three-dimensional model according to claim 10, wherein the solidification step comprises encapsulating the three-dimensional modeling composition in a mold having a desired shape and solidifying the composition. The solidification step
The first step of forming a film with the three-dimensional modeling composition and
The second step of solidifying the film formed in the first step and
The method for manufacturing a three-dimensional model according to claim 10, which comprises repeating the above a plurality of times. The solidification step
The first step of forming a film with the three-dimensional modeling composition and
The third step of forming the film by the curable support composition containing the curable support material at a position different from the position where the film by the three-dimensional modeling composition was formed, and
The fourth step of solidifying the film formed in the first step and the third step, and
The method for manufacturing a three-dimensional model according to claim 10, which comprises repeating the above a plurality of times.