WO2018159493A1 - Photocurable composition for solid molding, method for preparing solid article therewith, and resin - Google Patents

Abstract

This photocurable composition for solid molding contains: a (meth)acryl compound having a (meth)acryloyl group; and a photo-radical generator, the photocurable composition being characterized by containing a polyrotaxane having a plurality of cyclic molecules each having at least one among a (meth)acryloyl group and a hydroxyl group.

Description

Photocurable composition for three-dimensional modeling, manufacturing method of three-dimensional object using the same, and resin

The present invention relates to a photocurable composition for three-dimensional modeling, a method for producing a three-dimensional object using the same, and a resin.

An optical three-dimensional modeling method (an optical modeling method) for producing a desired three-dimensional object by curing a liquid photocurable composition for each layer with light such as ultraviolet rays and sequentially laminating them has been intensively studied. . The use of stereolithography is not limited to prototype modeling for rapid shape confirmation (rapid prototyping), but has expanded to include modeling of working models for functional verification and modeling of models (rapid tooling). In addition, the use of stereolithography is spreading to real product modeling (rapid manufacturing).

From such a background, the demand for the photocurable composition for three-dimensional modeling used in the stereolithography has been advanced. Recently, a photocurable composition for three-dimensional modeling that can model a three-dimensional object having high mechanical properties (strength, rigidity, toughness, etc.) comparable to general-purpose engineering plastics has been demanded.

In Patent Document 1, modeling (photocuring) is performed by an optical modeling method using a photocurable composition containing an acrylic group-containing blocked isocyanate and a chain extender, and the obtained photocured product is further heat treated. Describes a method of modeling a three-dimensional object by applying the above. Thereby, it is possible to model a three-dimensional object having higher strength and rigidity than the conventional photocurable composition, and it is possible to model a three-dimensional object having an excellent balance of strength, rigidity, and toughness.

International Publication No. 2015/200201

In Patent Document 1, the photocured material is heat-treated to reduce the crosslink density and to improve the toughness by generating polyurethane and polyurea. However, in the method described in Patent Document 1, the toughness of the obtained cured product was not sufficiently large.

Therefore, in view of the above-described problems, the present invention has an object to provide a photocurable composition for three-dimensional modeling that can form a three-dimensional object having higher toughness than before.

The photocurable composition for three-dimensional modeling as one aspect of the present invention includes a (meth) acrylic compound having a (meth) acryloyl group and a photoradical generator. And a polyrotaxane having a plurality of cyclic molecules having at least one of a (meth) acryloyl group and a hydroxyl group.

According to the photocurable composition for three-dimensional modeling as one aspect of the present invention, it is possible to provide a photocurable composition for three-dimensional modeling that can model a three-dimensional object having higher toughness than before.

It is a figure which shows typically the reaction scheme when irradiating light and hardening the photocurable composition which concerns on 1st Embodiment. It is a figure which shows typically the reaction scheme when making the photocurable composition in the case of the polyrotaxane which has a (meth) acryloyl group based on 2nd Embodiment irradiate with light, and to make it harden | cure. It is a figure which shows typically the reaction scheme at the time of irradiating light and hardening | curing the photocurable composition in case the polyrotaxane has a hydroxyl group based on 2nd Embodiment.

Hereinafter, embodiments of the present invention will be described. It should be noted that the present invention is not limited to the following embodiments, and is appropriately modified with respect to the following embodiments based on ordinary knowledge of those skilled in the art without departing from the spirit of the present invention. Those with improvements and the like are also included in the scope of the present invention.

(First embodiment)
The photocurable composition for three-dimensional modeling according to the present embodiment (hereinafter sometimes simply referred to as “photocurable composition”) includes a (meth) acrylic compound (a) that is a polymerizable compound, and a photoradical. A generator (b) and a polyrotaxane (c) are contained.

Hereinafter, each component contained in the photocurable composition according to the present embodiment will be described in detail.

[(Meth) acrylic compound (a)]
The meta (acrylic) compound (a) is a compound having at least one (meth) acryloyl group, and undergoes a polymerization reaction with radicals generated by the photoradical generator (b) described later.

Here, in this specification, “(meth) acryloyl group” means an acryloyl group or a methacryloyl group, and “(meth) acrylic compound” means an acrylic compound or a methacrylic compound.

The (meth) acrylic compound (a) may be composed of only one type of (meth) acrylic compound or may be composed of a plurality of types of (meth) acrylic compounds.

The number of (meth) acryloyl groups that the (meth) acrylic compound (a) has is not particularly limited. Examples of the (meth) acrylic compound (a) include a monofunctional (meth) acrylic compound having one (meth) acryloyl group in the molecule and a bifunctional (meth) having one (meth) acryloyl group in the molecule. Examples include acrylic compounds, trifunctional (meth) acrylic compounds having three (meth) acryloyl groups in the molecule, and tetrafunctional or more (meth) acrylic compounds having four or more (meth) acryloyl groups in the molecule. However, it is not limited to these.

The (meth) acrylic compound (a) may be a urethane (meth) acrylic compound having a urethane structure in the molecular structure or a polyester (meth) acrylic compound having a polyester structure in the molecular structure.

Specific examples of the (meth) acrylic compound (a) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (meth) acrylic. N-butyl acid, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylic N-heptyl acid, n-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate , Isodecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, ( T) Stearyl acrylate, (meth) acrylic acid tridecyl, (meth) acrylic acid tridecyl, (meth) acrylic acid cyclohexyl, (meth) acrylic acid isobornyl, (meth) acrylic acid dicyclopentanyl, (meth) acrylic acid adamantyl , Phenyl (meth) acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2-hydroxy (meth) acrylate Monofunctional (meth) acrylic compounds such as ethyl, 2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate; 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) Acrylate, 1,9-nonanediol di (meth) acrylate Tricyclodecane dimethanol (meth) acrylate, bisphenol A (poly) ethoxydi (meth) acrylate, bisphenol A (poly) propoxy di (meth) acrylate, bisphenol F (poly) ethoxydi (meth) acrylate, ethylene glycol di (meth) acrylate Bifunctional (meth) acrylic compounds such as: trimethylolpropane tri (meth) acrylate, trimethyloloctane tri (meth) acrylate, trimethylolpropane polyethoxytri (meth) acrylate, trimethylolpropane (poly) propoxytri (meth) Acrylate, trimethylolpropane (poly) ethoxy (poly) propoxytri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris [(meth) acrylic Royloxyethyl] isocyanurate, caprolactone-modified tris [(meth) acryloyloxyethyl] isocyanurate and other trifunctional (meth) acryl compounds; ditrimethylolpropane tetra (meth) acrylate, pentaerythritol polyethoxytetra (meth) acrylate, penta Erythritol polyethoxytetra (meth) acrylate, pentaerythritol (poly) propoxytetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipenta Examples include, but are not limited to, tetrafunctional or higher functional (meth) acrylic compounds such as erythritol hexa (meth) acrylate.

Specific examples of the urethane (meth) acrylic compound include polycarbonate urethane (meth) acrylate, polyester urethane (meth) acrylate, polyether urethane (meth) acrylate, caprolactone urethane (meth) acrylate, and the like. However, it is not limited to these.

These urethane (meth) acrylic compounds can be obtained by reacting an isocyanate compound obtained by reacting a polyol with a diisocyanate and a (meth) acrylate monomer having a hydroxyl group. Here, specific examples of the polyol include polycarbonate polyol, polyester polyol, polyether polyol, and polycaprolactone polyol.

The polyester (meth) acrylic compound is obtained, for example, by obtaining a polyester oligomer having hydroxyl groups at both ends by condensation of polycarboxylic acid and polyol, and then esterifying the hydroxyl groups at both ends with acrylic acid.

[Photoradical generator (b)]
The photoradical generator (b) is a compound that initiates a polymerization reaction by generating radicals that are polymerization factors by receiving active energy rays such as light having a predetermined wavelength. The photoradical agent (b) may be a compound that decomposes by receiving active energy rays to generate radicals. Here, specifically, as the active energy rays, charged particle beams such as infrared rays, visible rays, ultraviolet rays, far ultraviolet rays, X-rays, and electron beams, radiation, and the like can be used.

Specific examples of the photo radical generator (b) include benzoin, benzoin monomethyl ether, benzoin isopropyl ether, acetoin, benzyl, benzophenone, p-methoxybenzophenone, diethoxyacetophenone, benzyldimethylketal, Carbonyl such as 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, methylphenylglyoxylate, ethylphenylglyoxylate, 2-hydroxy-2-methyl-1-phenylpropan-1-one Compounds, sulfur compounds such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide, and acylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide. To but are not limited to.

Examples of commercially available photo radical generators include IRGACURE series such as IRGACURE (registered trademark) 184 and IRGACURE 819, DAROCUR series such as DAROCUR (registered trademark) 1173 and DAROCUR TPO (above, manufactured by BASF), KAYACURE (registered trademark) ) Examples include, but are not limited to, KAYACURE series (manufactured by Nippon Kayaku Co., Ltd.) such as DETX-S and KAYACURE CTX.

The addition amount of the photoradical generator (b) is preferably 0.05% by mass or more and 20% by mass or less, and more preferably 0.1% by mass or more when the entire photocurable composition is 100% by mass. More preferably, it is 5 mass% or less. When the addition amount is less than 0.05% by mass, the radicals to be generated are insufficient, and the polymerization conversion rate of the photocurable composition is reduced. As a result, the photocurable composition is obtained by photocuring and then heat-treating. The strength of the three-dimensional object is insufficient. When the added amount exceeds 30% by mass, most of the light irradiated to the photocurable composition is absorbed by the excessive photoradical generator (b), and light does not reach the inside of the curable composition. Sometimes. Therefore, there exists a possibility that the polymerization conversion rate of the photocurable composition inside a photocurable composition may fall.

[Polyrotaxane (c)]
The polyrotaxane (c) includes a plurality of cyclic molecules having at least one functional group selected from a (meth) acryloyl group and a hydroxyl group, a linear molecule penetrating through the plurality of cyclic molecules, A supramolecule having a blocking group disposed at both ends of a linear molecule and preventing elimination of the cyclic molecule. In the polyrotaxane (c), the cyclic molecule can move freely along the linear molecular chain like a pulley. In the polyrotaxane (c), the cyclic molecule is blocked by a blocking group at the end of the linear molecule, and thus has a structure that cannot escape from the linear molecule.

(Cyclic molecules of polyrotaxane)
The polyrotaxane cyclic molecule has at least one functional group selected from a (meth) acryloyl group and a hydroxyl group, can include a linear molecule, and is free along the linear molecular chain like a pulley. If it can move to, it will not be specifically limited. In addition, the cyclic molecule does not necessarily have to be a completely closed ring, and may be, for example, approximately “C”.

Specific examples of the polyrotaxane cyclic molecule include cyclodextrins such as α-cyclodextrin, β-cyclodextrin and γ-cyclodextrin, crown ethers, benzocrowns, dibenzocrowns, dicyclohexanocrowns, etc. However, it is not limited to these. Of these, cyclodextrins are preferred because they are readily available and it is easy to select an appropriate ring diameter. In particular, α-cyclodextrin is more preferably used as the cyclic molecule of polyrotaxane. The polyrotaxane (c) may contain two or more different types of cyclic molecules in one molecule of the polyrotaxane.

The polyrotaxane cyclic molecule has at least one functional group selected from a (meth) acryloyl group and a hydroxyl group, and has two or more (meth) acryloyl groups or a hydroxyl group alone or simultaneously. You may do it. When the polyrotaxane (c) contains two or more different types of cyclic molecules in one molecule of the polyrotaxane, at least one type of cyclic molecule has at least one (meth) acryloyl group or hydroxyl group. It only has to have.

(Linear molecule of polyrotaxane)
The polyrotaxane linear molecule is a molecule or substance that is included in a cyclic molecule and can be integrated without a covalent bond, and is not particularly limited as long as it is linear.

Here, “linear” in the present specification means substantially “linear”. That is, as long as the cyclic molecule can slide or move on the linear molecule, the linear molecule may have a branched chain. Further, as long as the cyclic molecule can slide or move on the linear molecule, it may be bent or spiral. Further, the length of the “straight chain” is not particularly limited as long as the cyclic molecule can slide or move on the linear molecule.

Specific examples of polyrotaxane linear molecules include polyalkylenes, polyesters such as polycaprolactone, polyethers such as polyalkylene glycols such as polyethylene glycol and polypropylene glycol, polyamides, polyacryls, and benzene rings. The linear molecule etc. which have are mentioned, However, It is not limited to these. Of these, polyethers are preferable from the viewpoint of easy inclusion of molecules and flexibility, and among these, polyethylene glycol is more preferable.

The number average molecular weight of the linear molecule of the polyrotaxane is preferably 1,000 or more and 1,000,000 or less, and more preferably 5,000 or more and 50,000 or less. When the molecular weight of the linear molecule is less than 1,000, the pulley effect due to the cyclic molecule cannot be sufficiently obtained, and the sufficient impact improvement effect cannot be obtained. When the molecular weight exceeds 1,000,000, the viscosity becomes too high, and there is a possibility that the photo-curable resin composition for optical three-dimensional modeling of the present invention cannot be modeled by the optical modeling apparatus.

(Blocking group)
The blocking group is arranged at the end (both ends) of the polyrotaxane linear molecule, and has a role of preventing the cyclic molecule from being detached from the linear molecule. The blocking group is not particularly limited as long as it has a role of a stopper for preventing the cyclic molecule from leaving. Examples of the method for preventing elimination include a method for physically preventing the use of a bulky group and a method for electrically preventing the use of an ionic group.

Specific examples of the blocking group include adamantane groups, dinitrophenyl groups, cyclodextrins, trityl groups, fluoresceins, pyrenes, and derivatives or modified products thereof. There is no limitation.

Examples of commercially available polyrotaxanes that can be used as the polyrotaxane (c) having a (meth) acryloyl group according to the present embodiment include, for example, SeRM SM3405P, SeRM SA3405P, SeRM SM3400C, SeRM SA3400C, SeRM SA2400C (all of these are advanced Soft Materials Co., Ltd.). Moreover, as a commercial item of the polyrotaxane (c) which has a hydroxyl group, SeRM SH3400P, SeRM SH2400P, SeRM SH1300P (all are the product made from Advanced Soft Materials Co., Ltd.) is mentioned, for example.

The blending ratio of the polyrotaxane (c) is not particularly limited as long as the effect of the present invention is not impaired. The blending ratio is, for example, preferably 1% by mass or more and 50% by mass or more preferably 5% by mass or more and 30% by mass or less when the entire photocurable composition is 100% by mass. When the blending ratio is less than 1% by mass, the toughness of a cured product obtained by curing the photocurable composition may be lowered. When the said mixture ratio exceeds 50 mass%, there exists a possibility that the elasticity modulus and intensity | strength of the hardened | cured material obtained by hardening | curing a photocurable composition may fall.

[Other ingredients]
(Radically polymerizable compound)
The photocurable composition according to this embodiment may further contain a radical polymerizable compound other than the (meth) acrylic compound. Examples of such radically polymerizable compounds include styrene monomers, styrene oligomers, acrylonitrile compounds, vinyl ester monomers, vinyl ester oligomers, N-vinyl pyrrolidone, acrylamide monomers, acrylamide oligomers, conjugated diene monomers. Conjugated diene oligomers, vinyl ketone monomers, vinyl ketone oligomers, vinyl halide monomers, vinyl halide oligomers, vinylidene halide monomers, vinylidene halide oligomers, etc. Absent.

(Cationically polymerizable compound)
The photocurable composition according to the present embodiment may further contain a cationic polymerizable compound. The cationic polymerizable compound undergoes a polymerization reaction with an acid generated by a photoacid generator described later.

Examples of the cationic polymerizable compound include, but are not limited to, epoxy monomers, epoxy oligomers, oxetane monomers, oxetane oligomers, vinyl ether monomers, vinyl ether oligomers, and the like.

(Photoacid generator)
The photocurable composition according to this embodiment may further contain a photoacid generator when it contains the above-described cationic polymerizable compound. The photoacid generator is a compound that initiates a polymerization reaction by generating an acid as a polymerization factor by receiving active energy rays such as light of a predetermined wavelength.

Specific examples of the photoacid generator include trichloromethyl-s-triazines, sulfonium salts and iodonium salts, quaternary ammonium salts, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. These are not limited.

When the photoacid generator is included, the addition amount of the photoacid generator is preferably 0.05% by mass or more and 20% by mass or less when the entire photocurable composition is 100% by mass. More preferably, the content is 1% by mass or more and 5% by mass or less. When the addition amount is less than 0.05% by mass, the acid generated is insufficient, and the polymerization conversion rate of the photocurable composition is decreased. As a result, the photocurable composition is heat-treated after being photocured. The strength of the three-dimensional object is insufficient. When the added amount exceeds 30% by mass, most of the light irradiated to the photocurable composition is absorbed by the excessive photoacid generator, and the light may not reach the inside of the curable composition. . Therefore, there exists a possibility that the polymerization conversion rate of the photocurable composition inside a photocurable composition may fall.

(Reaction accelerator)
When the chain extender (d) uses a compound having a hydroxyl group, or when using a polyrotaxane (c) having a hydroxyl group, it is preferable to add a reaction accelerator. The reaction accelerator is a compound characterized by accelerating the reaction between the isocyanate group formed by deblocking the blocked isocyanate group of the blocked isocyanate (a1) or the blocked isocyanate (a3) described later and the hydroxyl group. Examples of the reaction accelerator include tin compounds such as dibutyltin dilaurate, dioctyltin dilaurate, and dibutyltin dioctanoate.

These reaction accelerators (e) may be used alone or in combination of two or more. The amount of the reaction accelerator (e) used is preferably 0.001% by mass or more and 10% by mass or less with respect to 100% by mass of the total amount of polyol.

(Other additives)
The photocurable composition according to the present embodiment is a reactive diluent, a colorant such as a pigment or a dye, an antifoaming agent, a leveling agent, a thickener, as necessary, unless the effects of the present invention are impaired. Additives such as flame retardants, antioxidants, inorganic fillers (crosslinked polymer particles, silica, glass powder, ceramics powder, metal powders, etc.), modifying resins (thermoplastic resins, thermoplastic resin particles, rubber particles, etc.) 1 type or 2 types or more may be contained appropriately.

In addition, the photocurable composition according to the present embodiment can appropriately use a photoinitiator or a sensitizer in addition to the photoradical generator (b) as necessary. Examples of the photoinitiation assistant or sensitizer include benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, tertiary amine compounds, and xanthone compounds.

[Function of photocurable composition for three-dimensional modeling]
The photocurable composition for three-dimensional modeling containing a (meth) acrylic compound (a) and a photoradical generator (b) can be cured by irradiation with light to form a cured product (three-dimensional object). . At this time, radical polymerization reaction of the (meth) acrylic compound (a) is started by radicals generated by the photoradical generator (b), and curing of the photocurable composition proceeds. Here, in order to increase the rigidity of the cured product (three-dimensional object), it is preferable that the crosslink density in the cured product (three-dimensional object) is high. However, in the conventional photocurable composition for three-dimensional modeling, the crosslinking point in the cured product does not move. Therefore, if the crosslinking density is increased too much, the toughness is lowered and becomes brittle.

On the other hand, the photo-curable composition for three-dimensional modeling according to the present embodiment contains the polyrotaxane (c) described above. In the polyrotaxane (c) according to this embodiment, the cyclic molecule in the polyrotaxane (c) contains at least one functional group selected from a (meth) acryloyl group and a hydroxyl group.

When the cyclic molecule in the polyrotaxane (c) according to this embodiment contains a (meth) acryloyl group, when the photocurable composition according to this embodiment is irradiated with light, the (meth) acrylic compound (a) The polymerization reaction between them proceeds. In addition, a polymerization reaction between the (meth) acrylic compound (a) and the polyrotaxane (c) and a polymerization reaction between the polyrotaxanes (c) also proceed. As a result, a cured product (three-dimensional product) having a structure as schematically shown in FIG. Since the cyclic molecules in the polyrotaxane (c) can move freely along the linear molecular chain in the polyrotaxane (c), some cross-linking points in the cured product can move. In other words, even when external stress is applied, the cross-linking point can move in response to the stress. As a result, the tension between the polymers becomes uniform with respect to the stress, resulting in a tougher than conventional photocurable compositions. A cured product having a high thickness can be obtained.

When the cyclic molecule in the polyrotaxane (c) according to the present embodiment contains a hydroxyl group, when the photocurable composition according to the present embodiment is irradiated with light, polymerization of the (meth) acrylic compounds (a) is performed. The reaction proceeds. As a result, a cured product in which the (meth) acryloyl group in the molded article obtained and the hydroxyl group in the polyrotaxane (c) are bonded by hydrogen bonds is obtained. The internal stress generated during the curing by the post-treatment by heat is eliminated by the movement of the crosslinking point in the cured product and the optimal arrangement of the (meth) acryloyl group and the polyrotaxane (c). When a (meth) acryloyl group in the molded article is subjected to an external stress or the like via a hydrogen bond to a hydroxyl group of the cyclic molecule of the polyrotaxane (c), the stress can be transmitted. Since the cyclic molecule of the polyrotaxane (c) can move, the tension between the polymers can be made uniform with respect to the stress. As a result, as in the case where the cyclic molecule in the polyrotaxane (c) contains a (meth) acryloyl group, a cured product having higher toughness than the conventional photocurable composition can be obtained by the effect of the polyrotaxane. Become.

[Method of manufacturing a three-dimensional object]
The photocurable composition which concerns on this embodiment can be used suitably for the manufacturing method of the solid thing by the optical three-dimensional modeling method (optical modeling method). Hereinafter, the manufacturing method of the solid thing using the photocurable composition concerning this embodiment is demonstrated.

A conventionally known method can be used as the stereolithography. That is, in the method for producing a three-dimensional object according to this embodiment, the photocurable composition according to this embodiment is selectively irradiated with active energy rays such as light to cure the photocurable composition one by one. This is a method for producing a three-dimensional object by repeating this process.

In the step of curing the photocurable composition layer by layer, active energy rays are selectively irradiated to the photocurable composition based on slice data of the three-dimensional object to be created.

The active energy ray applied to the photocurable composition is not particularly limited as long as it is an active energy ray that can cure the photocurable composition according to the present embodiment. Specific examples of the active energy rays include electromagnetic waves such as ultraviolet rays, visible rays, infrared rays, X rays, gamma rays and laser rays, and particle rays such as alpha rays, beta rays and electron rays. Among these, ultraviolet rays are most preferable from the viewpoint of the absorption wavelength of the photoradical generator (c) to be used and the cost of equipment installation. The exposure amount is not particularly limited, preferably not 0.001J / cm ² or more 10J / cm ² or less. If it is less than 0.001 J / cm ² , the photocurable composition may not be sufficiently cured, and if it exceeds 10 J / cm ² , the irradiation time becomes longer and the productivity is lowered.

The method of irradiating the photocurable composition with active energy rays is not particularly limited. For example, when irradiating light as active energy rays, the following method can be employed. As a first method, there is a method of using two-dimensionally scanning light with respect to the photocurable composition using light condensed in a spot shape like laser light. At this time, the two-dimensional scanning may be a point drawing method or a line drawing method. As the second method, there is a surface exposure method in which light is applied to the shape of the cross-sectional data using a projector or the like. In this case, the active energy rays may be irradiated in a planar manner through a planar drawing mask formed by arranging a plurality of micro light shutters such as a liquid crystal shutter or a digital micromirror shutter.

In this step, after obtaining a shaped object by stereolithography, the surface of the obtained shaped object may be washed with a cleaning agent such as an organic solvent. Moreover, you may perform the postcure which hardens the unreacted residual component which may remain | survive on the surface or inside of a molded article by irradiating light and heat with respect to the obtained molded article.

(Second Embodiment)
The photocurable composition which concerns on this embodiment contains the block isocyanate (a1) which has the (meth) acryloyl group mentioned later as the polymeric compound (a) in 1st Embodiment. That is, when the polyrotaxane (c) has a (meth) acryloyl group, the photocurable composition according to the second embodiment includes a blocked isocyanate (a1) having a (meth) acryloyl group and a photo radical generator (b ), And a chain extender (d), and when the polyrotaxane (c) has a hydroxyl group, a blocked isocyanate (a1) having a (meth) acryloyl group, a photo radical generator (b), And a reaction accelerator (e).

Hereinafter, each component contained in the photocurable composition according to the present embodiment will be described in detail. In the following description, the description of the same parts as those in the first embodiment may be omitted.

[Blocked isocyanate (a1)]
The blocked isocyanate (a1) is represented by the following general formula (1).
ABC (1)
(In formula (1), A and C each independently represent a group represented by the following formula (2), and B represents a group represented by the following formula (3).

Here, in formula (2), R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an optionally substituted hydrocarbon group having 1 to 10 carbon atoms, and L ₁ represents a substituent. Represents a divalent hydrocarbon group having 1 to 10 carbon atoms which may have In formula (3), R ₃ and R ₄ each independently represent a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and a is an integer of 1 to 100. . )

In Formula (2) and Formula (3), when any of L ₁ , R ₂ , R ₃ and R ₄ has a substituent, the substituent may be a substituent containing a carbon atom. However, in that case, the atom to which the substituent is bonded to each of L ₁ , R ₂ , R ₃ and R ₄ is an atom other than a carbon atom. In that case, the number of carbon atoms contained in the substituent is not included in the number of carbon atoms of the “hydrocarbon group”. Moreover, the said substituent may contain the hetero atom.

Block isocyanate (a1) is a (meth) acrylic compound containing at least two (meth) acryloyl groups as described above.

In formula (2), R ₂ is preferably a group selected from a tert-butyl group, a tert-pentyl group, and a tert-hexyl group. This is preferable because the temperature (deblocking temperature) when the photocurable composition is photocured and then subjected to a heat treatment for deblocking can be reduced. Further, by adopting any one group of the R _2, it is possible to facilitate the synthesis of blocked isocyanate (a1). Further, by adopting any one group of the R _2, to obtain the synthesis of blocked isocyanate (a1) a low cost.

In formula (2), L ₁ is preferably an ethylene group or a propylene group from the viewpoint of availability and ease of synthesis.

In the formula (3), R ₃ has at least one divalent linking group selected from the group consisting of the following formulas (A-1) to (A-4) from the viewpoint of easy availability and synthesis. Is preferred.

Here, in the formula (A-1), c is an integer of 1 to 10, and in the formula (A-2), d is an integer of 1 to 10.

In the formula (3), _{R 3} is preferably has a group represented by the above formula (A-4). Thereby, the elasticity modulus of the hardened | cured material obtained by making it harden | cure can be raised.

In the formula (1), A and C are preferably the same. That is, the blocked isocyanate (a1) is preferably represented by the following general formula (4). Thereby, the synthesis | combination of block isocyanate (a1) can be made cheap and easy.
ABA ... (4)
(In formula (4), A represents a group represented by the above formula (2), and B represents a group represented by the above formula (3).)

Specific examples of the blocked isocyanate (a1) include the following structures.

The blocked isocyanate (a1) contained in the photocurable composition may be one type of compound or a plurality of types of compounds. When a plurality of types of compounds are contained as the blocked isocyanate (a1), the blending ratio of the blocked isocyanate (a1) in the photocurable composition is calculated based on the total mass of the plurality of types of compounds. And

The blending ratio of the blocked isocyanate (a1) in the photocurable composition is preferably 10% by mass or more and 90% by mass or less, and 30% by mass or more and 70% by mass, when the entire photocurable composition is 100% by mass. It is more preferable that the amount is not more than mass%. When the blending ratio is less than 10% by mass, the toughness of the cured product obtained by curing the photocurable composition becomes low, and when the blending ratio exceeds 80% by mass, the viscosity of the photocurable composition is high. It becomes difficult to handle.

<Synthesis Method of Blocked Isocyanate (a1)>
Next, a method for synthesizing the blocked isocyanate (a1) will be described. The blocked isocyanate (a1) includes the following step (I) and step (II).
Step (I): Step of reacting polyol and diisocyanate Step (II): Step of reacting a blocking agent with diisocyanate having a polyol skeleton obtained in step (I)

Hereinafter, each process will be described.

(Step (I): Step of reacting polyol and diisocyanate)
This step is a step of reacting polyol and diisocyanate. Thereby, a polyisocyanate having a polyol skeleton is obtained.

Examples of the polyol used in this step include polyether polyol, polyester polyol, polycarbonate polyol, polyalkylene polyol, and polyacetal, but are not limited thereto. Two or more of these polyols may be mixed and used.

Examples of diisocyanates used in this step include aliphatic diisocyanates such as trimethylene diisocyanate, 1,2-propylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, trimethylhexamethylene diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, 3- Cycloaliphatic diisocyanates such as isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isophorodiisocyanate), methylene bis (cyclohexyl isocyanate) or dicyclohexylmethane diisocyanate, bis (isocyanate methyl) cyclohexane, norbornane diisocyanate, phenylene diisocyanate, Li diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethane diisopropyl Société sulfonates, although other aromatic diisocyanates such as 4,4'-toluidine diisocyanate, but are not limited to.

In this step, the polyol and the diisocyanate are preferably reacted in a solvent. The said solvent will not be specifically limited if a polyol and diisocyanate melt | dissolve. Specifically, dialkyl ethers such as diethyl ether and dipropyl ether, cyclic ethers such as 1,4-dioxane and tetrahydrofuran, ketones such as acetone, methyl ethyl ketone, diisopropyl ketone and isobutyl methyl ketone, methyl acetate and ethyl acetate And esters such as butyl acetate, hydrocarbons such as toluene, xylene and ethylbenzene, halogen solvents such as methylene chloride, chloroform, carbon tetrachloride, tetrachloroethane, trichloroethane and chlorobenzene, and nitriles such as acetonitrile. These solvents may be used alone or in combination of two or more. The solvent to be used is preferably a dehydrated solvent from the viewpoint of suppressing decomposition of the isocyanate group of diisocyanate by moisture.

The ratio of the number of moles of diisocyanate to the number of moles of polyol to be reacted in this step (number of moles of diisocyanate / number of moles of polyol) is preferably 1 or more and 20 or less, and more preferably 3 or more and 10 or less. When the ratio is less than 1, the ratio of the unwanted side formation of polyurethane by the polyaddition reaction of diisocyanate and polyol, which is a side reaction, increases, and the yield of diisocyanate having the target polyol skeleton decreases. If the ratio is greater than 20, unreacted diisocyanate remains excessively after the reaction, and it may be difficult to remove the unreacted diisocyanate.

This step is preferably performed in an inert atmosphere such as nitrogen, helium or argon. Further, this step is preferably performed at 0 ° C. or higher and 150 ° C. or lower, and more preferably performed at 30 ° C. or higher and 100 ° C. or lower. Moreover, you may perform this process under recirculation | reflux. If this step is carried out at a reaction temperature higher than 150 ° C., the possibility of causing side reactions increases. When this step is carried out at a reaction temperature of less than 0 ° C., the reaction rate decreases, so there is a concern that the reaction time may be extended or the yield may be reduced.

Note that this step may be performed in the presence of a catalyst. Examples of the catalyst include, for example, organic tin compounds such as tin octylate, dibutyltin diacetate, dibutyltin dilaurate and 2-ethylhexanetin, naphthenic acid metal salts such as copper naphthenate, zinc naphthenate and cobalt naphthenate, triethylamine, benzyl And tertiary amines such as dimethylamine, pyridine, N, N-dimethylpiperazine, and triethylenediamine. These catalysts may be used alone or in combination of two or more. The amount of the catalyst used is preferably 0.001% by mass to 10% by mass with respect to 100% by mass of the total amount of polyol.

The diisocyanate having a polyol skeleton obtained in this step can be separated and purified by a conventional separation method, for example, separation means such as reprecipitation with a poor solvent, concentration and filtration, or a separation means combining these.

(Step (II): a step of reacting a blocking agent with a diisocyanate having a polyol skeleton obtained in step (I))
This step is a step of reacting the blocking agent with the polyisocyanate having the polyol skeleton obtained in step (I). Thereby, the blocked isocyanate which concerns on this embodiment is obtained.

Here, the blocking agent is a compound capable of protecting an active isocyanate group by reacting with an isocyanate group (—NCO) of diisocyanate. Isocyanate groups protected by a blocking agent are called blocked isocyanate groups or blocked isocyanate groups. Since the blocked isocyanate group is protected by the blocking agent, it can be kept stable in a normal state.

When the blocked isocyanate compound having a blocked isocyanate group is heated, the blocking agent is dissociated (deblocked) from the blocked isocyanate group, and the original isocyanate group can be regenerated.

The blocking agent used in this step is not particularly limited as long as it is a (meth) acrylic compound having an amino group, but tert-butylaminoethyl (meth) acrylate, tert-pentylaminoethyl (meth) acrylate, tert-hexylamino A compound selected from ethyl (meth) acrylate and tert-butylaminopropyl (meth) acrylate is preferable. Thereby, the deblocking temperature of blocked isocyanate can be lowered.

In this step, it is preferable to react a blocking agent and a diisocyanate having a polyol skeleton in a solvent. The solvent is not particularly limited as long as the blocking agent and the polyisocyanate having a polyol skeleton are dissolved, and specifically, those described in the step (I) can be used.

This step is preferably performed in an inert atmosphere such as nitrogen, helium or argon. Further, this step is preferably performed at 0 ° C. or higher and 150 ° C. or lower, more preferably 30 ° C. or higher and 80 ° C. or lower. Moreover, you may perform this process under recirculation | reflux. When this step is carried out at a reaction temperature of less than 0 ° C., the reaction is difficult to proceed. Moreover, when this process is performed at reaction temperature higher than 150 degreeC, there exists a possibility that block agents may superpose | polymerize by the polymerization reaction of a (meth) acryloyl group. As a result, the yield may decrease.

Note that this step may be performed in the presence of a catalyst. As specific examples of the catalyst, those described in the step (I) can be used.

In this step, a polymerization inhibitor may be used for the purpose of suppressing polymerization of the (meth) acryloyl group of the blocking agent. Specific examples include benzoquinone, hydroquinone, catechol, diphenylbenzoquinone, hydroquinone monomethyl ether, naphthoquinone, t-butylcatechol, t-butylphenol, dimethyl-t-butylphenol, t-butylcresol, dibutylhydroxytoluene and phenothiazine.

The blocked isocyanate obtained in this step can be separated and purified by the same method as in step (I).

[Chain extender (d)]
The chain extender (d) is a compound having at least two active hydrogens that react with an isocyanate group formed by deblocking a blocked isocyanate group of the blocked isocyanate (a1) or the blocked isocyanate (a3) described later.

Examples of active hydrogen that reacts with an isocyanate group include a hydrogen atom in a hydroxyl group, a hydrogen atom in an amino group, and a hydrogen atom in a thiol group. Therefore, the chain extender (d) preferably contains a compound having at least two of the same or different functional groups selected from the group consisting of a hydroxyl group, an amino group, and a thiol group in one molecule. From the viewpoint of reactivity, the chain extender (d) is at least selected from the group consisting of a polyol having at least two hydroxyl groups, a polyamine having at least two amino groups, and a polythiol having at least two thiol groups. It is more preferable to contain one. In particular, when the chain extender (d) having a hydroxyl group is used, the reaction accelerator (e) described later is preferably used from the viewpoint of reactivity.

Specific examples of the chain extender (d) include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, Linear diols such as 1,9-nonanediol and 1,10-decanediol; 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2,2-diethyl- 1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2,4-heptanediol, 1,4-dimethylolhexane, 2-ethyl-1,3-hexanediol, 2, 2,4-trimethyl-1,3-pentanediol, 2-methyl-1,8-octanediol, 2-butyl-2-ethyl-1,3-propanediol, dimer Diols having branched chains such as diols; Diols having ether groups such as diethylene glycol and propylene glycol; Alicyclic structures such as 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and 1,4-dihydroxyethylcyclohexane Diols having an aromatic group such as xylylene glycol, 1,4-dihydroxyethylbenzene, 4,4′-methylenebis (hydroxyethylbenzene); polyols such as glycerin, trimethylolpropane, pentaerythritol; N -Hydroxyamines such as methylethanolamine and N-ethylethanolamine; ethylenediamine, 1,3-diaminopropane, hexamethylenediamine, triethylenetetramine, diethylenetriamine, iso Rondiamine, 4,4'-diaminodicyclohexylmethane, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine, di-2-hydroxypropylethylenediamine, 4 , 4′-diphenylmethanediamine, methylenebis (o-chloroaniline), xylylenediamine, diphenyldiamine, tolylenediamine, hydrazine, piperazine, polyamines such as N, N′-diaminopiperazine; 1,2-ethanedithiol, 1 , 2,3-propanetrithiol, 1,2-cyclohexanedithiol, bis (2-mercaptoethyl) ether, tetrakis (mercaptomethyl) methane, diethylene glycol bis (2- Mercaptoacetate), trimethylolpropane tris (3-mercaptopropionate), trimethylolpropane tris (2-mercaptoacetate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), Aliphatic acids such as hydroxymethyl sulfide bis (2-mercaptoacetate), hydroxymethyl sulfide bis (3-mercaptopropionate), 1,1,3,3-tetrakis (mercaptomethylthio) propane, tris (mercaptoethylthio) methane Polythiols; 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-bis (mercaptomethyl) benzene, 1,3-bis (merca) Tomethyl) benzene, 1,4-bis (mercaptomethyl) benzene, 1,2-bis (mercaptoethyl) benzene, 1,3-bis (mercaptoethyl) benzene, 1,4-bis (mercaptoethyl) benzene, 1, 3,5-trimercaptobenzene, 1,3,5-tris (mercaptomethyl) benzene, 1,3,5-tris (mercaptomethyleneoxy) benzene, 1,3,5-tris (mercaptoethyleneoxy) benzene, 2 Aromatic polythiol compounds such as 1,5-toluenedithiol, 3,4-toluenedithiol, 1,5-naphthalenedithiol, 2,6-naphthalenedithiol; and water. These chain extenders may be used alone or in combination of two or more.

Among these, the balance of the physical properties of a cured product obtained by heat-curing the photocurable composition after photocuring as described later is preferable, and it is industrially inexpensive and available in large quantities. 4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,4-cyclohexanedimethanol, 1, 4-Dihydroxyethylcyclohexane, ethylenediamine, 1,3-diaminopropane, isophoronediamine, and 4,4′-diaminodicyclohexylmethane are preferred.

The ratio of the number of moles of chain extender (d) to the number of moles of blocked isocyanate (a1) (number of moles of chain extender (d) / number of moles of blocked isocyanate (a1)) is 0.1 or more and 5 or less. It is preferably 0.5 or more and 3 or less. As will be described later, when the photocurable composition according to this embodiment is photocured and then heat treated, the isocyanate group is regenerated, and a bond such as a urethane bond is formed between the isocyanate group and the chain extender (d). Reaction occurs. However, if the ratio is less than 0.1, the efficiency of the reaction between the isocyanate group and the chain extender (d) is low, and the mechanical properties of the three-dimensional product finally obtained by heat treatment after photocuring Tend to decrease. On the other hand, if the ratio is larger than 5, unreacted excess chain extender (d) remains inside the three-dimensional object, and the mechanical properties of the three-dimensional object finally obtained by heat treatment after photocuring deteriorates. There is a tendency.

[Reaction accelerator (e)]
In the present embodiment, as described above, the polyrotaxane having at least one functional group selected from a (meth) acryloyl group and a hydroxyl group is contained. When the chain extender (d) uses a compound having a hydroxyl group, or when a polyrotaxane (c) having a hydroxyl group is used, the reaction accelerator (e) removes the blocked isocyanate group of the blocked isocyanate (a1). It is a compound characterized by accelerating the reaction between an isocyanate group formed by blocking and a hydroxyl group. Examples of the reaction accelerator include tin compounds such as dibutyltin dilaurate, dioctyltin dilaurate, and dibutyltin dioctanoate.

These reaction accelerators (e) may be used alone or in combination of two or more. The amount of the reaction accelerator (e) used is preferably 0.001% by mass or more and 10% by mass or less with respect to 100% by mass of the total amount of polyol.

[Functions of the photocurable composition]
Since the photocurable composition for three-dimensional modeling according to the present embodiment contains a polyrotaxane (c) having at least one functional group selected from a (meth) acryloyl group and a hydroxyl group, the first embodiment. Similarly, when cured by irradiation with light, a cured product (three-dimensional product) with higher toughness than before can be obtained.

Also, the photocurable composition for three-dimensional modeling according to the present embodiment can be further improved in toughness by being cured by being irradiated with light (photocuring) and then subjected to heat treatment. This reaction scheme will be described with reference to FIG. FIG. 2 is a diagram schematically showing a reaction scheme when the photocurable composition according to this embodiment is cured by irradiating light and then subjected to heat treatment.

When a polyrotaxane having a (meth) acryloyl group is used, a photo radical generator in the photocurable composition is obtained by irradiating the photocurable composition according to the present embodiment with light of a predetermined wavelength (for example, ultraviolet rays). (B) generates radicals. Then, the (meth) acryloyl group possessed by the blocked isocyanate (a1) undergoes a polymerization reaction and solidifies. At this time, the polymerization reaction between the polyrotaxane (c) having a (meth) acryloyl group and the blocked isocyanate (a1) also proceeds. In addition, when the photocurable composition further contains a reactive diluent such as another radical polymerizable compound, the three components of blocked isocyanate (a1), polyrotaxane (c) and reactive diluent are appropriately combined. The polymerization reaction proceeds. Thereby, a photocured material as schematically shown in FIG. 2B is generated. Since this photocured product can move a cross-linking point as in the first embodiment, the photocured composition has higher toughness than the case where the photocurable composition does not contain polyrotaxane (c).

Next, when the obtained photocured product is subjected to a heat treatment, as schematically shown in FIG. 2 (C), deblocking in which the block part (BL) derived from the blocking agent proceeds, Isocyanate groups (—NCO) are regenerated. Then, the regenerated isocyanate group immediately reacts with the chain extender (d). Thereby, when the chain extender (d) has a hydroxyl group, a urethane bond is generated by the effect of the reaction accelerator (e), and the chain extender (d) has an amino group. A urea bond is formed in. As a result, a cured product schematically shown in FIG. 2 (D) is obtained.

On the other hand, when a polyrotaxane having a hydroxyl group is used, when the photocurable composition according to this embodiment is irradiated with light having a predetermined wavelength (for example, ultraviolet rays), a photo radical generator (b) in the photocurable composition (b) ) Generates radicals. Then, the (meth) acryloyl group possessed by the blocked isocyanate (a1) undergoes a polymerization reaction and solidifies. In addition, when the photocurable composition further contains a reactive diluent such as another radical polymerizable compound, a polymerization reaction proceeds by appropriately combining the two components of the blocked isocyanate (a1) and the reactive diluent. To do. As a result, a photocured product as schematically shown in FIG. 3B is generated.

Next, when the obtained photocured product is subjected to a heat treatment, as schematically shown in FIG. 3 (C), deblocking in which the block part (BL) derived from the blocking agent proceeds, Isocyanate groups (—NCO) are regenerated. Then, the regenerated isocyanate group reacts immediately with the hydroxyl group of the polyrotaxane (c) by the effect of the reaction accelerator (e), and a urethane bond is generated. Since this photocured product can move a cross-linking point as in the first embodiment, the photocured composition has higher toughness than the case where the photocurable composition does not contain polyrotaxane (c).

As a result, a cured product schematically shown in FIG. 3 (D) is obtained.

As described above, in the photocurable composition according to this embodiment, by performing heat treatment after photocuring, the crosslink density is reduced more than after photocuring due to deblocking as described above. be able to. And a urethane bond or a urea bond produces | generates, and the hardened | cured material which has a polyurethane structure or a polyurea structure, and those mixed structures produces | generates. As a result, the toughness can be further improved.

It is known that the degree to which the toughness of a cured product obtained by curing the curable composition by adding a toughness improving component to the curable composition is affected by the crosslink density of the cured product. . That is, the effect of improving toughness due to the toughness improving component is reduced in a cured product having a high crosslinking density, and conversely, the effect of improvement is increased in a cured product having a low crosslinking density. In the present embodiment, by using the blocked isocyanate (a1) having a (meth) acryloyl group as the polymerizable compound (a), as described above, a photocured product is obtained by a deblocking reaction by performing a heat treatment after photocuring. The bond inside can be broken. That is, by performing heat treatment, the crosslink density of the cured product can be lowered. Therefore, according to the present embodiment, since the crosslinking density can be reduced by performing heat treatment as compared with a general photocured product, the toughness improving effect by the polyrotaxane (c), which is a toughness improving component, is exhibited more greatly. can do.

(Light-thermoset)
A cured product (photo-thermosetting product) obtained by photocuring the photocurable composition according to this embodiment and then heat-treating will be described. The photo-thermoset (resin) according to the present embodiment includes a repeating structural unit represented by the following general formula (8), a repeating structural unit represented by the following general formula (9), and a polyrotaxane structure. contains.

Here, in formula (8), R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an optionally substituted hydrocarbon group having 1 to 10 carbon atoms, and L ₁ represents a substituent. Represents a divalent hydrocarbon group having 1 to 10 carbon atoms which may have In the formula (9), R ₃ , R ₄ and R ₅ each independently represent a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and X ₁ and X ₂ are each Independently, one of O (oxygen atom), S (sulfur atom), and NH (imino group) is represented. a is an integer of 1 or more and 100 or less.

In Formula (8) and Formula (9), when any of L ₁ , R ₂ , R ₃ , R ₄ and R ₅ has a substituent, the substituent is a substituent containing a carbon atom, Also good. However, in that case, the atom to which the substituent is bonded to each of L ₁ , R ₂ , R ₃ , R ₄ and R ₅ is an atom other than a carbon atom. In that case, the number of carbon atoms contained in the substituent is not included in the number of carbon atoms of the “hydrocarbon group”. Moreover, the said substituent may contain the hetero atom.

In Formula (8), R ₂ is a group selected from a tert-butyl group, a tert-pentyl group, and a tert-hexyl group because the deblocking temperature can be lowered as described above. Is preferred. In addition, by adopting any of the above groups as R ₂ , the synthesis of the photo-thermosetting product can be facilitated at low cost.

In formula (8), L ₁ is preferably an ethylene group or a propylene group from the viewpoint of availability and ease of synthesis.

In formula (9), R ₃ has at least one divalent linking group selected from the group consisting of the following formulas (A-1) to (A-4) from the viewpoint of easy availability and synthesis. Is preferred.

Here, in the formula (A-1), c is an integer of 1 to 10, and in the formula (A-2), d is an integer of 1 to 10.

In Formula (9), R ₃ preferably has a group represented by Formula (A-4). Thereby, the elastic modulus of the photo-thermosetting product can be increased.

Here, the “polyrotaxane structure” means a plurality of cyclic molecules, a linear molecule penetrating the plurality of cyclic molecules in a skewered manner, and the elimination of the cyclic molecules arranged at both ends of the linear molecule. And a blocking group that prevents the above. The cyclic molecule, linear molecule, and blocking group are as described above.

In the photo-thermosetting material according to the present embodiment, the repeating structural unit represented by the general formula (8) is bonded to the cyclic molecule in the polyrotaxane structure. The cyclic molecule in the polyrotaxane structure can freely move along the linear molecule in the polyrotaxane structure. Therefore, when an external stress is applied, the cross-linking point in the cured product can move in accordance with the stress. As a result, the tension between the polymers becomes uniform with respect to the stress. -Thermosets show high toughness.

[Method of manufacturing a three-dimensional object]
The photocurable composition which concerns on this embodiment can be used suitably for the manufacturing method of the solid thing by the optical three-dimensional modeling method (optical modeling method). Hereinafter, the manufacturing method of the solid thing using the photocurable composition concerning this embodiment is demonstrated.

The manufacturing method of the three-dimensional object which concerns on this embodiment has the process of modeling a modeling object by the optical modeling method, and the process of heat-processing the said modeling object.

<Process of modeling a model by stereolithography>
A conventionally known method can be used as the optical modeling method. This step includes a step of selectively irradiating the photocurable composition with active energy rays based on slice data of a three-dimensional object to be created to cure the photocurable composition layer by layer.

There is no restriction | limiting in particular as an active energy ray irradiated to a photocurable composition in this process, if it is an active energy ray which can harden the photocurable composition which concerns on this embodiment. Specific examples of the active energy rays include electromagnetic waves such as ultraviolet rays, visible rays, infrared rays, X rays, gamma rays and laser rays, and particle rays such as alpha rays, beta rays and electron rays. Among these, ultraviolet rays are most preferable from the viewpoint of the absorption wavelength of the photoradical generator (c) to be used and the cost of equipment installation. The exposure amount is not particularly limited, preferably not 0.001J / cm ² or more 10J / cm ² or less. If it is less than 0.001 J / cm ² , the photocurable composition may not be sufficiently cured, and if it exceeds 10 J / cm ² , the irradiation time becomes longer and the productivity is lowered.

The method of irradiating the photocurable composition with active energy rays is not particularly limited. For example, when irradiating light as active energy rays, the following method can be employed. As a first method, there is a method of using two-dimensionally scanning light with respect to the photocurable composition using light condensed in a spot shape like laser light. At this time, the two-dimensional scanning may be a point drawing method or a line drawing method. As the second method, there is a surface exposure method in which light is applied to the shape of the cross-sectional data using a projector or the like. In this case, the active energy rays may be irradiated in a planar manner through a planar drawing mask formed by arranging a plurality of micro light shutters such as a liquid crystal shutter or a digital micromirror shutter.

In this step, after obtaining a shaped object by stereolithography, the surface of the obtained shaped object may be washed with a cleaning agent such as an organic solvent. Moreover, you may perform the postcure which hardens the unreacted residual component which may remain | survive on the surface or inside of a molded article by irradiating light and heat with respect to the obtained molded article. In addition, when performing post cure by heat irradiation, you may serve as the process of heat-processing to the molded article mentioned later.

<Process of heat-treating the model>
In the present embodiment, heat treatment is performed on a modeled object obtained by the optical modeling method to advance deblocking as described above to reduce the crosslinking density and to generate polyurethane or polyurea. Thereby, a three-dimensional object with higher toughness can be formed.

The heat treatment temperature in this step is not particularly limited as long as it is a temperature at which deblocking of the block portion in the molded article proceeds, but is preferably 50 ° C. or higher and 200 ° C. or lower. More preferably, it is 100 degreeC or more and 150 degrees C or less. If it is lower than 50 ° C., deblocking does not proceed, and the effect of improving toughness may not be sufficiently obtained. When it exceeds 200 ° C., the resin is deteriorated, and various mechanical properties of the three-dimensional object may be lowered.

The heat treatment time in this step is not particularly limited as long as the deblocking of the block part in the shaped article proceeds sufficiently, but is preferably 0.5 hours or more and 10 hours or less. If it is shorter than 0.5 hour, deblocking does not proceed, and the effect of improving toughness may not be sufficiently obtained. If it is longer than 10 hours, it is disadvantageous from the viewpoints of reduction in various mechanical properties of the three-dimensional object due to deterioration of the resin and productivity.

(Third embodiment)
The photocurable composition which concerns on this embodiment contains the blocked isocyanate (a2) which has the (meth) acryloyl group mentioned later as the blocked isocyanate (a1) in 2nd Embodiment. That is, in the photocurable composition according to the third embodiment, when the polyrotaxane has a (meth) acryloyl group, the blocked isocyanate (a3), the photoradical generator (b), the polyrotaxane (c), and the chain And an extender (d). On the other hand, when the polyrotaxane has a hydroxyl group, it contains a blocked isocyanate (a3), a photo radical generator (b), a polyrotaxane (c), and a reaction accelerator (e).

Hereinafter, each component contained in the photocurable composition according to the present embodiment will be described in detail.

In the following description, description of the same parts as those in the first embodiment and the second embodiment may be omitted.

[Block isocyanate (a2)]
The blocked isocyanate (a2) is represented by the following general formula (5).
A-D-C (5)
(In formula (5), A and C each independently represent a group represented by the following formula (2), and D represents a group represented by the following formula (6).

Here, in formula (2), R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an optionally substituted hydrocarbon group having 1 to 10 carbon atoms, and L ₁ represents a substituent. Represents a divalent hydrocarbon group having 1 to 10 carbon atoms which may have In formula (6), R ₁₁ , R ₁₂ and R ₁₃ each independently represent a divalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. E and f are integers satisfying 1 ≦ e + f ≦ 50, either one of which may be 0. )

In Formula (2) and Formula (6), when any of L ₁ , R ₂ , R ₁₁ , R ₁₂ and R ₁₃ has a substituent, the substituent is a substituent containing a carbon atom, Also good. However, in that case, the atom to which the substituent is bonded to each of L ₁ , R ₂ , R ₁₁ , R ₁₂ and R ₁₃ is an atom other than a carbon atom. In that case, the number of carbon atoms contained in the substituent is not included in the number of carbon atoms of the “hydrocarbon group”.

In formula (2), R ₂ is preferably a group selected from a tert-butyl group, a tert-pentyl group, and a tert-hexyl group. This is preferable because the temperature (deblocking temperature) when the photocurable composition is photocured and then subjected to a heat treatment for deblocking can be reduced. Further, by adopting any one group of the R _2, it is possible to facilitate the synthesis of blocked isocyanate (a2). Further, by adopting any one group of the R _2, to obtain the synthesis of blocked isocyanate (a2) at low cost.

In formula (2), L ₁ is preferably an ethylene group or a propylene group from the viewpoint of availability and ease of synthesis.

In the formula (6), R ₁₁ and R ₁₂ are preferably each independently any one of the following formulas (B-1) to (B-9). Thereby, the elastic modulus and intensity | strength of the hardened | cured material obtained by heat-processing after photocuring a photocurable composition so that it may mention later can be made still higher.

Here, in formula (B-1), g is an integer of 1 to 10, and in formula (B-2), either h or i may be 0, and is an integer satisfying 1 ≦ h + i ≦ 10 is there. In formula (B-3), either j or k may be 0, and is an integer that satisfies 1 ≦ j + k ≦ 10.

In formula (5), A and C are preferably the same. That is, the blocked isocyanate (a2) is preferably represented by the following general formula (7). Thereby, the synthesis | combination of block isocyanate (a2) can be made cheap and easy.
AD-A ... (7)
(In the formula (7), A represents a group represented by the above formula (2), and D represents a group represented by the above formula (6).)

Specific examples of the blocked isocyanate (a2) include the following structures.

<Synthesis Method of Blocked Isocyanate (a3)>
Next, a method for synthesizing the blocked isocyanate (a3) will be described. The method for synthesizing the blocked isocyanate (a3) includes the following step (I) ′ and step (II).
Step (I) ′: Step of reacting polycarbonate diol and diisocyanate Step (II): Step of reacting the blocking agent with the diisocyanate having the polycarbonate skeleton obtained in step (I)

Since step (I) ′ is the same as in step (I) of the second embodiment except that polycarbonate diol is used instead of polyol, description of portions overlapping with those of the second embodiment will be omitted.

The polycarbonate diol used in this step can be synthesized by, for example, a transesterification reaction between a carbonate compound and a diol.

Examples of carbonate compounds used to synthesize polycarbonate diol include dialkyl carbonates such as dimethyl carbonate and diethyl carbonate, alkylene carbonates such as ethylene carbonate and propylene carbonate, diphenyl carbonate, dinaphthyl carbonate, dianthryl carbonate, and diphenanthryl. Examples thereof include diaryl carbonates such as carbonate, diindanyl carbonate, and tetrahydronaphthyl carbonate, but are not limited thereto. Two or more of these carbonate compounds may be mixed and used.

Examples of the diol used for synthesizing the polycarbonate diol include ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 3-methyl-1 , 5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 2-methyl-1,8-octanediol, 1,9-nonanediol and other aliphatic diols, cyclohexanediol, hydrogenated bisphenol -A, hydrogenated bisphenol-F, hydrogenated xylylene cholole, and other alicyclic diols, bisphenol-A, bisphenol-F, 4,4'-biphenol, xylylene glycol, and other aromatic diols, etc. But only It is not. Two or more of these diols may be mixed and used.

The number average molecular weight M _n of the polycarbonate diol is preferably 100 or more and 5000 or less. When the number average molecular weight _{Mn of the} polycarbonate diol is less than 100, the molecular weight of the finally obtained blocked isocyanate is reduced, and the elastic modulus and strength of the three-dimensional product obtained by curing the photocurable composition are reduced. There is. Moreover, when the number average molecular weight _{Mn of} polycarbonate diol exceeds 5000, the molecular weight of the finally obtained blocked isocyanate will become large, the viscosity of a photocurable composition may become high, and workability | operativity may fall.

Examples of commercially available polycarbonate diols include ETERNACOLL (registered trademark) UM-90 (3/1) (M _n = 900), ETERNACOLL UM-90 (1/1) (M _n = 900), and ETERNACOLL UM-90. (1/3) (M _n = 900), ETERNACOLL UC-100 (M _n = 1000), ETERNACOLL UH-200 (M _n = 2000), ETERNCOLLUH-100 (M _n = 1000), ETERNACOLL PH-200 ( M _n = 2000) and ETERNACOLL PH-100 (M _n = 1000) (all of which are manufactured by Ube Industries, Ltd.), but are not limited thereto.

[Chain extender (d)]
When the photocurable composition which concerns on this embodiment has a (meth) acryloyl group on a polyrotaxane (c) similarly to the photocurable composition which concerns on 2nd Embodiment, chain extender (d) is used. contains. The description about the chain extender (d) according to this embodiment is the same except that the blocked isocyanate (a1) is replaced with the blocked isocyanate (a3) in the description of the chain extender (d) according to the second embodiment. Therefore, the description is omitted.

[Reaction accelerator (e)]
Similar to the reaction accelerator according to the second embodiment, the reaction accelerator according to this embodiment is added as necessary. That is, when the chain extender (d) has a hydroxyl group, a polyrotaxane is contained when (c) has a hydroxyl group. The explanation about the reaction accelerator (e) according to this embodiment is the same except that the blocked isocyanate (a1) is replaced with the blocked isocyanate (23) in the description of the chain extender (d) according to the second embodiment. Therefore, the description is omitted.

(Light-thermoset)
A cured product (photo-thermosetting product) obtained by photocuring the photocurable composition according to this embodiment and then heat-treating will be described. The photo-thermoset (resin) according to the present embodiment includes a repeating structural unit represented by the following general formula (8), a repeating structural unit represented by the following general formula (10), and a polyrotaxane structure. contains.

Here, in formula (8), R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an optionally substituted hydrocarbon group having 1 to 10 carbon atoms, and L ₁ represents a substituent. Represents a divalent hydrocarbon group having 1 to 10 carbon atoms which may have In the formula (10), R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ each independently represents a divalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, ₃ and X ₄ each independently represent one of O (oxygen atom), S (sulfur atom), and NH (imino group), and either e or f may be 0, 1 ≦ e + f ≦ An integer satisfying 50.

In Formula (8) and Formula (10), when any of L ₁ , R ₂ , R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ has a substituent, the substituent is a substituent containing a carbon atom. It may be. However, in that case, the atom to which the substituent is bonded to each of L ₁ , R ₂ , R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ is an atom other than a carbon atom. In that case, the number of carbon atoms contained in the substituent is not included in the number of carbon atoms of the “hydrocarbon group”.

In Formula (8), R ₂ is a group selected from a tert-butyl group, a tert-pentyl group, and a tert-hexyl group because the deblocking temperature can be lowered as described above. Is preferred. In addition, by adopting any of the above groups as R ₂ , the synthesis of the photo-thermosetting product can be facilitated at low cost.

In formula (8), L ₁ is preferably an ethylene group or a propylene group from the viewpoint of availability and ease of synthesis.

In the formula (10), R ₁₁ and R ₁₂ are preferably each independently any one of the following formulas (B-1) to (B-9). Thereby, the elastic modulus and strength of the photo-thermoset can be further increased.

Here, in formula (B-1), g is an integer of 1 to 10, and in formula (B-2), either h or i may be 0, and is an integer satisfying 1 ≦ h + i ≦ 10 is there. In formula (B-3), either j or k may be 0, and is an integer that satisfies 1 ≦ j + k ≦ 10.

Here, the “polyrotaxane structure” means a plurality of cyclic molecules, a linear molecule penetrating the plurality of cyclic molecules in a skewered manner, and the elimination of the cyclic molecules arranged at both ends of the linear molecule. And a blocking group that prevents the above. The cyclic molecule, linear molecule, and blocking group are as described above.

In the photo-thermoset according to the present embodiment, in the case of a polyrotaxane having a (meth) acryloyl group, the repeating structural unit represented by the general formula (8) is bonded to a cyclic molecule in the polyrotaxane structure. Yes. The cyclic molecule in the polyrotaxane structure can freely move along the linear molecule in the polyrotaxane structure. Therefore, when an external stress is applied, the cross-linking point in the cured product can move in accordance with the stress. As a result, the tension between the polymers becomes uniform with respect to the stress. -Thermosets show high toughness.

When the cyclic molecule in the polyrotaxane (c) according to the present embodiment contains a hydroxyl group, when the photocurable composition according to the present embodiment is irradiated with light, polymerization of the (meth) acrylic compounds (a) is performed. The reaction proceeds. Curing by reacting the isocyanate group formed by deblocking the blocked isocyanate group of the blocked isocyanate (a2) described later and the hydroxyl group in the polyrotaxane (c) by subjecting the resulting molded article to a heat treatment. A thing is obtained. Due to the effect of the polyrotaxane, a cured product having higher toughness than the conventional photocurable composition can be obtained.

(Fourth embodiment)
The photocurable composition according to this embodiment contains a blocked isocyanate (a3) having a branched chain structure as the polymerizable compound (a) in the first embodiment. That is, the photocurable composition according to this embodiment comprises a blocked isocyanate (a3) having a branched chain structure, a photo radical generator (b), a polyrotaxane (c), and a chain extender (d). contains.

The blocked isocyanate having a branched chain structure is a (meth) acrylic compound containing at least three (meth) acryloyl groups. Specific examples of the blocked isocyanate having a branched chain structure include a blocked isocyanate represented by the following general formula (A).

In formula (4), A ₁ to A ₄ are each independently a structure represented by the following general formula (12), and B is a structure represented by the following general formula (13).

In General Formula (12), R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an optionally substituted hydrocarbon group having 1 to 10 carbon atoms, and L ₁ has a substituent. And a divalent hydrocarbon group having 1 to 10 carbon atoms which may be present. In the general formula (13), R _3a , R _3b , R ₄ , R ₅ , R ₆ and R ₇ are each independently a divalent divalent having 1 to 20 carbon atoms which may have a substituent. Represents a hydrocarbon group, Y ₁ represents a divalent linking group, and a represents an integer of 1 to 99. It said _{R 4} is same as _{R 4} in the formula (3).

In General Formula (12) and General Formula (13), when any of L ₁ , R ₂ , R _3a , R _3b , R ₄ , R ₅ , R ₆ and R ₇ has a substituent, the substitution The group may be a substituent containing a carbon atom. However, in that case, the atom to which the substituent is bonded to each of L ₁ , R ₂ , R _3a , R _3b , R ₄ , R ₅ , R ₆ and R ₇ is an atom other than a carbon atom. In that case, the number of carbon atoms contained in the substituent is not included in the number of carbon atoms of the “hydrocarbon group”. It said _{R 4} is same as _{R 4} in the formula (3).

In general formula (12), R ₂ is preferably a group selected from a tert-butyl group, a tert-pentyl group, and a tert-hexyl group. This is preferable because the temperature (deblocking temperature) when the photocurable composition is photocured and then subjected to a heat treatment for deblocking can be reduced. Further, by adopting any one group of the R _2, it is possible to facilitate the synthesis of blocked isocyanate. Further, by adopting any one group of the R _2, to obtain the synthesis of blocked isocyanate at a low cost.

In general formula (12), L ₁ is preferably an ethylene group or a propylene group from the viewpoint of availability and ease of synthesis.

In general formula (13), Y ₁ is preferably at least one divalent linking group selected from the group consisting of the following formulas (C1) to (C3) from the viewpoint of easy availability and synthesis.

In the general formula (11), A ₁ to A ₄ are preferably the same. That is, the blocked isocyanate is preferably represented by the following general formula (6). Thereby, the synthesis | combination of block isocyanate can be made cheap and easy.

In general formula (14), A represents a group represented by general formula (12), and B represents a group represented by general formula (13).

The blending ratio of the blocked isocyanate (a3) having a branched chain structure in the photocurable composition is preferably 0 part by mass or more and 90% by mass or less when the entire photocurable composition is 100%. More preferably, it is at least part% and no more than 70% by mass. When the said mixture ratio exceeds 80%, the viscosity of a photocurable composition will become high and handling will become difficult.

Specific examples of the blocked isocyanate include blocked isocyanates represented by the following formulas (I-1) to (I-20).

<Synthesis Method of Blocked Isocyanate (a3)>
Next, a method for synthesizing the blocked isocyanate (a3) having a branched chain structure will be described. The method for synthesizing the blocked isocyanate (a3) includes the following step (I) and step (II).
Step (I): Step of reacting a polyol and diisocyanate Step (II): Step of reacting a blocking agent with a polyisocyanate having a polyol skeleton obtained in Step (I)

Hereinafter, each process will be described.

(Step (I): Step of reacting polyol and diisocyanate)
This step is a step of reacting polyol and diisocyanate. Thereby, a polyisocyanate having a polyol skeleton is obtained.

Examples of the polyol used in this step include polyether polyol, polyester polyol, polycarbonate polyol, polyalkylene polyol, and polyacetal, but are not limited thereto. Two or more of these polyols may be mixed and used.

Examples of diisocyanates used in this step include aliphatic diisocyanates such as trimethylene diisocyanate, 1,2-propylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, trimethylhexamethylene diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, 3- Cycloaliphatic diisocyanates such as isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isophorodiisocyanate), methylenebis (cyclohexyl isocyanate) or dicyclohexylmethane diisocyanate, bis (isocyanatomethyl) cyclohexane, norbornane diisocyanate, phenylene diisocyanate, Li diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethane diisopropyl Société sulfonates, although other aromatic diisocyanates such as 4,4'-toluidine diisocyanate, but are not limited to.

In this step, the polyol and the diisocyanate are preferably reacted in a solvent. The said solvent will not be specifically limited if a polyol and diisocyanate melt | dissolve. Specifically, dialkyl ethers such as diethyl ether and dipropyl ether, cyclic ethers such as 1,4-dioxane and tetrahydrofuran, ketones such as acetone, methyl ethyl ketone, diisopropyl ketone and isobutyl methyl ketone, methyl acetate and ethyl acetate And esters such as butyl acetate, hydrocarbons such as toluene, xylene and ethylbenzene, halogen solvents such as methylene chloride, chloroform, carbon tetrachloride, tetrachloroethane, trichloroethane and chlorobenzene, and nitriles such as acetonitrile. These solvents may be used alone or in combination of two or more. The solvent to be used is preferably a dehydrated solvent from the viewpoint of suppressing decomposition of the isocyanate group of the diisocyanate compound by moisture.

The ratio of the number of moles of diisocyanate to the number of moles of polyol to be reacted in this step (number of moles of diisocyanate / number of moles of polyol) is preferably 1 or more and 20 or less, and more preferably 3 or more and 10 or less. When the ratio is less than 1, the ratio of the unwanted addition of polyurethane by the polyaddition reaction of diisocyanate and polyol, which is a side reaction, increases, and the yield of polyisocyanate having the target polyol skeleton decreases. If the ratio is greater than 20, unreacted diisocyanate remains excessively after the reaction, and it may be difficult to remove the unreacted diisocyanate.

This step is preferably performed in an inert atmosphere such as nitrogen, helium or argon. Further, this step is preferably performed at 0 ° C. or higher and 150 ° C. or lower, and more preferably performed at 30 ° C. or higher and 100 ° C. or lower. Moreover, you may perform this process under recirculation | reflux. If this step is carried out at a reaction temperature higher than 150 ° C., the possibility of causing side reactions increases. If this step is carried out at a reaction temperature of less than 0 ° C., the reaction rate decreases, so the reaction time becomes longer or the yield decreases.

Note that this step may be performed in the presence of a catalyst. Examples of the catalyst include, for example, organic tin compounds such as tin octylate, dibutyltin diacetate, dibutyltin dilaurate and 2-ethylhexanetin, naphthenic acid metal salts such as copper naphthenate, zinc naphthenate and cobalt naphthenate, triethylamine, benzyl And tertiary amines such as dimethylamine, pyridine, N, N-dimethylpiperazine, and triethylenediamine. These catalysts may be used alone or in combination of two or more. The amount of the catalyst used may be 0.001% by mass or more and 1% by mass or less with respect to 100% by mass of the total amount of polyol.

The diisocyanate having a polyol skeleton obtained in this step can be separated and purified by a conventional separation method, for example, separation means such as reprecipitation with a poor solvent, concentration and filtration, or a separation means combining these.

(Step (II): a step of reacting a blocking agent with a polyisocyanate having a polyol skeleton obtained in step (I))
This step is a step of reacting the blocking agent with the polyisocyanate having the polyol skeleton obtained in step (I). Thereby, the blocked isocyanate (a3) having a branched structure according to the present embodiment is obtained.

Here, the blocking agent is a compound capable of protecting an active isocyanate group by reacting with an isocyanate group (—NCO) of diisocyanate. Isocyanate groups protected by a blocking agent are called blocked isocyanate groups or blocked isocyanate groups. Since the blocked isocyanate group is protected by the blocking agent, it can be kept stable in a normal state.

When the blocked isocyanate compound having a blocked isocyanate group is heated, the blocking agent is dissociated (deblocked) from the blocked isocyanate group, and the original isocyanate group can be regenerated.

The blocking agent used in this step is not particularly limited as long as it is a (meth) acrylic compound having an amino group, but tert-butylaminoethyl (meth) acrylate, tert-pentylaminoethyl (meth) acrylate, tert-hexyl. A compound selected from aminoethyl (meth) acrylate and tert-butylaminopropyl (meth) acrylate is preferred. Thereby, the deblocking temperature of blocked isocyanate can be lowered.

In this step, it is preferable to react a blocking agent and a diisocyanate having a polyol skeleton in a solvent. The solvent is not particularly limited as long as the blocking agent and the polyisocyanate having a polyol skeleton are dissolved. Specifically, those described in the description of the step (I) can be used.

This step is preferably performed in an inert atmosphere such as nitrogen, helium or argon. Further, this step is preferably performed at 0 ° C. or higher and 150 ° C. or lower, and more preferably performed at 30 ° C. or higher and 120 ° C. or lower. In order to obtain the blocked isocyanate (a3) having a branched structure, it is particularly preferable to treat at 60 ° C. or more and 100 ° C. or less. Moreover, you may perform this process under recirculation | reflux. When this step is carried out at a reaction temperature of less than 0 ° C., the reaction is difficult to proceed. Moreover, when this process is performed at reaction temperature higher than 150 degreeC, there exists a possibility that block agents may superpose | polymerize by the polymerization reaction of a (meth) acryloyl group.

Note that this step may be performed in the presence of a catalyst. As specific examples of the catalyst, those described in the description of the step (I) can be used.

In this step, a polymerization inhibitor may be used for the purpose of suppressing the polymerization reaction of the (meth) acryloyl group of the blocking agent. Specific examples include benzoquinone, hydroquinone, catechol, diphenylbenzoquinone, hydroquinone monomethyl ether, naphthoquinone, t-butylcatechol, t-butylphenol, dimethyl-t-butylphenol, t-butylcresol, dibutylhydroxytoluene and phenothiazine.

The blocked isocyanate obtained in this step can be separated and purified by the same method as in step (I).

By adding the photo radical generator (b), polyrotaxane (c), and chain extender (d) described in the second embodiment to the blocked isocyanate (a3) having a side chain structure, a photocurable composition is obtained. You can get things. When the polyrotaxane (c) has a hydroxyl group, the same reaction accelerator (e) as in the second embodiment may be added.

When manufacturing a three-dimensional object using the photocurable composition concerning this embodiment, the modeling method similar to the 1st and 2nd embodiment is employable.

As described above, the three-dimensional product produced using the photocurable composition according to the present embodiment can move the cross-linking point according to the stress even when an external stress is applied due to the effect of the polyrotaxane. As a result, the tension between the polymers becomes uniform with respect to the stress, and as a result, a cured product having higher toughness than the conventional photocurable composition can be obtained. Furthermore, the photocurable composition which concerns on this embodiment contains block isocyanate (a3). The blocked isocyanate (a3) may have a polycarbonate structure containing a plurality of carbonate groups (—O— (C═O) —O—) in the molecular structure as represented by the above formula (3). Therefore, when the cured product obtained by heat-curing the photocurable composition according to the present embodiment also includes the above-described polycarbonate structure therein, according to the photocurable composition according to the present embodiment, A three-dimensional object having high tensile strength and elastic modulus can be formed by stereolithography.

(Use)
The use of the photocurable composition for three-dimensional modeling according to the first to third embodiments and the cured product thereof is not particularly limited. For example, it can be used for various applications such as resin for stereolithography 3D printers, sports equipment, medical / nursing care equipment, industrial machinery / equipment, precision equipment, electrical / electronic equipment, electrical / electronic parts, building materials. is there.

Examples are given below to describe the present invention in detail, but the present invention is not limited to these examples. In addition, the identification of the compound performed in the Example and the comparative example and the tracking of the reaction were measured by the method described below.

(1) Identification of Compound 15 mg of a sample was dissolved in 1.1 g of deuterated chloroform (CDCl ₃ ), and ¹ H-NMR measurement was performed using a nuclear magnetic resonance apparatus JNM-ECA-400 (manufactured by JEOL).

(2) Reaction tracking (confirmation of disappearance of isocyanate groups)
The sample was measured by the ATR method (total reflection measurement method) using a Fourier transform infrared spectrometer (Spectrum One manufactured by Perkin Elmer), and the vertical axis was the absorbance, and the presence or absence of a peak near 2260 cm ⁻¹ derived from the isocyanate group was confirmed. did.

(Synthesis Example 1) Synthesis of blocked isocyanate 1

Based on the above scheme, blocked isocyanate 1 was synthesized. First, polytetrahydrofuran (M _n = 650) (100 g, 154 mmol, 1.0 eq.) And hexamethylene diisocyanate (207 g, 1.23 mol, 1.0 eq.) Were added to a 500 mL reactor at room temperature in an argon atmosphere and stirred. . To this solution was added 2-ethylhexane tin (II) (80 μL, cat.). The solution was heated to 50 ° C. and stirred at the same temperature for 5 hours. The solution was allowed to cool to room temperature and then added to vigorously stirred hexane (4 L). After stirring for 15 minutes, the mixture was allowed to stand for 15 minutes, and the upper layer (hexane layer) was removed by decantation. This operation was further repeated twice, and the lower layer (intermediate layer) was concentrated to obtain 170 g of polytetrahydrofuran diisocyanate 1.

The resulting polytetrahydrofuran diisocyanate 1 was added with 300 mL of dichloromethane and cooled with ice while stirring. Hydroquinone (10 mg) and 2- (t-butylamino) ethyl methacrylate (142 g, 769 mmol, 5.0 eq.) Were slowly added thereto, and the mixture was stirred at room temperature for 12 hours. This solution was analyzed by infrared spectroscopy, and it was confirmed by the above method that there was no isocyanate-derived absorption peak.

Next, the above solution was slowly added to hexane (4 L) that was vigorously stirred, stirred as it was for 20 minutes, and then allowed to stand for 20 minutes, and the upper hexane layer was removed by decantation. This operation was repeated three more times, and the lower layer, which was the target product, was filtered through Celite and then concentrated under high vacuum to obtain blocked isocyanate 1 (184 g) as a colorless viscous liquid.

(Synthesis Example 2) Synthesis of blocked isocyanate 2

Based on the above scheme, blocked isocyanate 2 was synthesized. First, polytetrahydrofuran (M _n = 650) (80 g, 123 mmol, 1.0 eq.), 4,4′-methylenebis (cyclohexyl diisocyanate) (323 g, 1.23 mol, at room temperature in a 500 mL reactor at room temperature. 1.0 eq.) Was added and stirred. To this solution was added 2-ethylhexane tin (II) (80 μL, cat.). The solution was heated to 50 ° C. and stirred at the same temperature for 5 hours. The solution was allowed to cool to room temperature and then added to vigorously stirred hexane (4 L). After stirring for 15 minutes, the mixture was allowed to stand for 15 minutes, and the upper layer (hexane layer) was removed by decantation. This operation was further repeated twice, and the lower layer (intermediate layer) was concentrated to obtain 126 g of polytetrahydrofuran diisocyanate 2.

The resulting polytetrahydrofuran diisocyanate 2 was added with 300 mL of dichloromethane and cooled with ice while stirring. Hydroquinone (10 mg) and 2- (t-butylamino) ethyl methacrylate (114 g, 615 mmol, 5.0 eq.) Were slowly added thereto and stirred at room temperature for 1.5 days. This solution was analyzed by infrared spectroscopy, and it was confirmed by the above method that there was no isocyanate-derived absorption peak.

Next, the above liquid was slowly added to hexane (4 L) that was vigorously stirred, stirred as it was for 20 minutes, and then allowed to stand for 20 minutes, and the upper hexane layer was removed by decantation. This operation was repeated three more times, and the lower layer, which was the target product, was filtered through Celite and then concentrated under high vacuum to obtain blocked isocyanate 2 (124 g) as a colorless viscous liquid.

(Synthesis Example 3) Synthesis of blocked isocyanate 3

Based on the above scheme, blocked isocyanate 3 was synthesized. First, hexamethylene diisocyanate (168 g, 0.1 mol, 10 eq.), Polycarbonate diol (etheracolum-90 1/1) (90 g, 0.1 mol, 1.0 eq. (M) at room temperature in an argon atmosphere in a 300 mL reactor. _n = 900)), 2-ethylhexane tin (II) (70 μL, cat.) was added. The solution was heated to 50 ° C. and stirred at the same temperature for 3 hours, and then slowly added dropwise to hexane (3 L) vigorously stirred while warm. After stirring for 20 minutes as it was, it was allowed to settle and the upper hexane layer was removed. The washing operation with hexane was further performed twice, and then the resulting viscous liquid was concentrated under high vacuum to obtain polycarbonate diisocyanate (151 g) as a colorless viscous liquid.

Dichloromethane (300 mL) and hydroquinone (20 mg) were added to the obtained polycarbonate diisocyanate, and then 2- (t-butylamino) ethyl methacrylate (92.6 g, 0.5 mol, 5) was maintained at 5 ° C. using a cooling bath. 0.0 eq.) Was slowly added dropwise. Thereafter, the cooling bath was removed and the mixture was stirred at room temperature for 14 hours. This solution was analyzed by infrared spectroscopy, and the disappearance of the isocyanate-derived absorption peak was confirmed by the above method.

Next, the above solution was slowly dropped into hexane (3 L) that was vigorously stirred. After completion of the dropwise addition, the mixture was stirred for 30 minutes, and the mixture was allowed to stand. Thereafter, the upper hexane layer was removed by decantation, and the same operation was performed once again. The resulting viscous liquid was dried under high vacuum at 40 ° C. for 6 hours to obtain blocked isocyanate 3 (215 g) which was a colorless very viscous liquid.

(Synthesis Example 4) Synthesis of blocked isocyanate 4

Based on the above scheme, blocked isocyanate 4 was synthesized. First, polytetrahydrofuran (100 g, 154 mmol, 1.0 eq.) And hexamethylene diisocyanate (207 g, 1.23 mol, 8.0 eq.) Having a number average molecular weight _Mn of 650 at room temperature in an argon atmosphere in a 500 mL reactor. Added and stirred. To this solution was added tin (II) 2-ethylhexanoate (80 μL, cat.). The solution was heated to 80 ° C. and stirred at the same temperature for 8 hours. The solution was allowed to cool to room temperature and then added to vigorously stirred hexane (4 L). After stirring for 15 minutes, the mixture was allowed to stand for 15 minutes, and the upper layer (hexane layer) was removed by decantation. This operation was further repeated twice, and the lower layer was concentrated to obtain 170 g of polytetrahydrofuran tetraisocyanate.

The resulting polytetrahydrofuran tetraisocyanate was added with 300 mL of dichloromethane and cooled with ice while stirring. Hydroquinone (10 mg) and 2- (t-butylamino) ethyl methacrylate (227 g, 1.23 mol, 8.0 eq.) Were slowly added thereto, and the mixture was stirred at room temperature for 12 hours. This solution was analyzed by infrared spectroscopy, and it was confirmed by the above method that there was no isocyanate-derived absorption peak.

Next, the above solution was slowly added to hexane (4 L) that was vigorously stirred, stirred as it was for 20 minutes, and then allowed to stand for 20 minutes, and the upper hexane layer was removed by decantation. This operation was repeated three more times, and the lower layer, which was the target product, was filtered through Celite and then concentrated under high vacuum to obtain blocked isocyanate 4 (184 g) as a colorless viscous liquid.

Example 1
First, the photocurable composition A was prepared according to the following prescription.
Polymerizable compound (a):
<A-1> Isobornyl methacrylate 39.7% by mass
<A-2> Block isocyanate 1 53.3 mass%
Photoradical generator (b):
<B-1> Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide 0.7% by mass
Chain extender (d):
<D-1> 4,4′-methylene-bis (cyclohexylamine) 6.3% by mass

Next, according to the following prescription, the photocurable composition 1 for three-dimensional modeling of Example 1 was prepared.
-Photocurable composition A 90 mass%
Polyrotaxane (c):
<C-1> SeRM SA2400C (manufactured by Advanced Soft Materials Co., Ltd.) 10.0% by mass

(Comparative Example 1)
A photocurable composition 2 for three-dimensional modeling of Comparative Example 1 was prepared in the same manner as in Example 1 except that the polyrotaxane (c) was not used in Example 1. That is, the composition of the photocurable composition 2 for three-dimensional modeling of Comparative Example 1 is the same as the composition of the photocurable composition A in Example 1.

(Example 2)
First, the photocurable composition B was prepared according to the following prescription.
Polymerizable compound (a):
<A-1> Isobornyl methacrylate 39.7% by mass
<A-3> Block isocyanate 2 53.3% by mass
Photoradical generator (b): bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide 0.7% by mass
Chain extender (d): 4,4′-diaminodiphenylmethane 6.3% by mass

Next, according to the following prescription, the photocurable composition 3 for three-dimensional modeling of Example 2 was prepared.
Photocurable composition B 90% by mass
Polyrotaxane (c):
<C-1> SeRM SA2400C (manufactured by Advanced Soft Materials Co., Ltd.) 10.0% by mass

(Comparative Example 2)
A photocurable composition 4 for three-dimensional modeling of Comparative Example 2 was prepared in the same manner as in Example 2 except that the polyrotaxane (c) was not used in Example 2. That is, the composition of the photocurable composition 4 for three-dimensional modeling in Comparative Example 2 is the same as the composition of the photocurable composition B in Example 2.

(Example 3)
First, a photocurable resin C was prepared according to the following formulation.
Polymerizable compound (a):
<A-1> Isobornyl methacrylate 39.7% by mass
<A-4> Blocked isocyanate 3 53.3 mass%
Photoradical generator (b):
<B-1> Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide 0.7% by mass
Chain extender (d):
<D-1> 4,4′-diaminodiphenylmethane 6.3% by mass

Next, according to the following prescription, the photocurable composition 5 for three-dimensional modeling of Example 3 was prepared.
-Photocurable composition C 90% by mass
Polyrotaxane (c):
<C-1> SeRM SA2400C (manufactured by Advanced Soft Materials Co., Ltd.) 10.0% by mass

(Comparative Example 3)
In Example 3, the photocurable composition 6 for three-dimensional modeling of the comparative example 3 was prepared like Example 3 except not using a polyrotaxane (c). That is, the composition of the photocurable composition 6 for three-dimensional modeling in Comparative Example 3 is the same as the composition of the photocurable composition C in Example 3.

Example 4
First, according to the following prescription, the photocurable resin D was prepared.
Polymerizable compound (a):
<A-1> Isobornyl methacrylate 39.1% by mass
<A-4> Block isocyanate 1 49.7% by mass
Photoradical generator (b):
<B-1> Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide 0.6% by mass
<Reaction accelerator> Dibutyltin dilaurate 0.6% by mass

Next, according to the following prescription, the photocurable composition 7 for three-dimensional modeling of Example 4 was prepared.
-Photocurable composition D 90 mass%
Polyrotaxane (c):
<C-2> SeRM SH1310P (manufactured by Advanced Soft Materials Co., Ltd.) 10.0% by mass

(Comparative Example 4)
A photocurable composition 8 for three-dimensional modeling of Comparative Example 4 was prepared in the same manner as in Example 4 except that no reaction accelerator was used in Example 4. That is, the composition of the three-dimensional photocurable composition 8 of Comparative Example 4 is the same as the composition of the photocurable composition C in Example 4.

(Example 5)
First, according to the following prescription, the photocurable resin E was prepared.
Polymerizable compound (a):
<A-1> Isobornyl methacrylate 35.7% by mass
<A-5> Branched-chain blocked isocyanate 4 48.0% by mass
Photoradical generator (b):
<B-1> Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide 0.6% by mass
Chain extender (d):
<D-1> 4,4′-diaminodiphenylmethane 5.7% by mass

Next, according to the following prescription, the photocurable composition 9 for three-dimensional modeling of Example 5 was prepared.
-Photocurable composition C 90% by mass
Polyrotaxane (c):
<C-1> SeRM SA2400C (manufactured by Advanced Soft Materials Co., Ltd.) 10.0% by mass

(Performance evaluation of photocurable composition for three-dimensional modeling)
Using each of the prepared photocurable compositions 1 to 6 for three-dimensional modeling, a cured product was produced by the following method. First, a 300 μm spacer was sandwiched between two quartz glasses, and the photocurable composition was poured into a gap having a width of 300 μm. Irradiate the poured photocurable composition with ultraviolet rays of 7 mW / cm ² for 120 seconds (total energy of 840 mJ / cm ² ) with an ultraviolet irradiation machine (trade name “UV LIGHT SOURCE EX250” manufactured by HOYA-SCHOTT). A photocured product was obtained.

The obtained photocured product was placed in a heating oven at 125 ° C. and heat-treated for 4 hours to obtain a photo-thermoset product.

Next, the obtained photo-thermoset having a thickness of about 300 μm was punched out into a No. 8 type dumbbell to prepare a test piece. This test piece was measured according to JIS K 7127 using a tensile tester (trade name “Strograph EII” manufactured by Toyo Seiki Seisakusho) at a test temperature of 23 ° C. and a tensile speed of 10 mm / min. Maximum point strength and elongation were measured. The breaking energy was determined from the area surrounded by the stress-strain curve obtained in this tensile test. The tensile modulus can be used as an index of rigidity, the maximum point strength can be used as an index of strength, and the breaking energy can be used as an index of toughness.

Table 1 summarizes each composition of the photo-curable composition for three-dimensional modeling and the mechanical properties of the light-thermosetting material produced using the composition.

(Summary of results)
As shown in Table 1, when Comparative Example 1 and Example 1, Comparative Example 2 and Example 2, and Comparative Example 3 and Example 3 are respectively compared, polyrotaxane (c) having a (meth) acryloyl group is contained. As a result, the breaking energy could be increased without lowering the elastic modulus and the maximum point strength. That is, according to the present invention, it was possible to improve toughness (breaking energy) while maintaining rigidity (elastic modulus) and strength (maximum point strength) at high levels. Moreover, when this block polyurethane was used, when Example 4 and Comparative Example 1 were compared, when it has a hydroxyl group, the break energy could be increased by including a polyrotaxane. When Example 4 and Comparative Example 4 were compared and a polyrotaxane containing a hydroxyl group was used, the toughness (breaking energy) was greater when a reaction accelerator was added.

In Example 5, as compared with Comparative Example 1, polyrotaxane was added to a blocked isocyanate having a branched chain structure, but the toughness (breaking energy) could be improved while maintaining a high elastic modulus. .

The present invention is not limited to the above embodiment, and various changes and modifications can be made without departing from the spirit and scope of the present invention. Therefore, in order to make the scope of the present invention public, the following claims are attached.

This application claims priority based on Japanese Patent Application No. 2017-040855 filed on Mar. 3, 2017 and Japanese Patent Application No. 2017-140151 filed on Jul. 19, 2017. All the descriptions are incorporated herein.

Claims (20)

A (meth) acryl compound having a (meth) acryloyl group and a photoradical generator, a photocurable composition for three-dimensional modeling,
A photocurable composition for three-dimensional modeling, comprising a polyrotaxane having a plurality of cyclic molecules having at least one of a (meth) acryloyl group or a hydroxyl group. The (meth) acrylic compound is represented by the following general formula (1)
ABC (1)
(In formula (1), A and C each independently represent a group represented by the following formula (2), and B represents a group represented by the following formula (3).

(In Formula (2), R ₁ represents a hydrogen atom or a methyl group, R ₂ represents a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and L ₁ has a substituent. And a divalent hydrocarbon group having 1 to 10 carbon atoms which may be substituted, and in formula (3), R ₃ and R ₄ each have 1 carbon atom which may have a substituent. To 20 hydrocarbon groups, and a is an integer of 1 or more and 100 or less.)
Containing a blocked isocyanate represented by
The polyrotaxane has a (meth) acryloyl group;
The photocurable composition for three-dimensional modeling according to claim 1, further comprising a chain extender. The (meth) acrylic compound is represented by the following general formula (1)
ABC (1)
(In formula (1), A and C each independently represent a group represented by the following formula (2), and B represents a group represented by the following formula (3).

(In Formula (2), R ₁ represents a hydrogen atom or a methyl group, R ₂ represents a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and L ₁ has a substituent. And a divalent hydrocarbon group having 1 to 10 carbon atoms which may be substituted, and in formula (3), R ₃ and R ₄ each have 1 carbon atom which may have a substituent. To 20 hydrocarbon groups, and a is an integer of 1 or more and 100 or less.)
Containing a blocked isocyanate represented by
The polyrotaxane has a hydroxyl group;
The photocurable composition for three-dimensional modeling according to claim 1, further comprising a reaction accelerator. The formula (3), wherein R ₃ has at least one divalent linking group selected from the group consisting of the following formulas (A-1) to (A-4): The photocurable composition for three-dimensional modeling of description.

(In formula (A-1), c is an integer of 1 to 10, and in formula (A-2), d is an integer of 1 to 10.) The blocked isocyanate has the following general formula (4)
ABA ... (4)
The photocurable composition for three-dimensional model | molding of any one of Claim 2 to 4 characterized by the above-mentioned. The (meth) acrylic compound has the following general formula (5)
A-D-C (5)
(In formula (5), A and C each independently represent a group represented by the following formula (2), and D represents a group represented by the following formula (6).

Here, in formula (2), R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an optionally substituted hydrocarbon group having 1 to 10 carbon atoms, and L ₁ represents a substituent. Represents a divalent hydrocarbon group having 1 to 10 carbon atoms which may have In formula (6), R ₁₁ , R ₁₂ and R ₁₃ each independently represent a divalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and a and b are , Either one may be 0, an integer satisfying 1 ≦ a + b ≦ 50. )
Containing a blocked isocyanate group represented by
The photocurable composition for three-dimensional modeling according to claim 1, further comprising a chain extender. 7. The light for three-dimensional modeling according to claim 6, wherein R ₁₁ and R ₁₂ are each independently any one of the following formulas (B-1) to (B-9) in the formula (6): Curable composition.

(In Formula (B-1), g is an integer of 1 to 10, and in Formula (B-2), either h or i may be 0, and is an integer satisfying 1 ≦ h + i ≦ 10, In formula (B-3), either j or k may be 0, and is an integer that satisfies 1 ≦ j + k ≦ 10.) The blocked isocyanate is represented by the following general formula (7)
AD-A ... (7)
The photocurable composition for three-dimensional modeling of Claim 6 or Claim 7 characterized by the above-mentioned. In the formula (2), R ₂ is a group selected from a tert-butyl group, a tert-pentyl group, and a tert-hexyl group. The photocurable composition for three-dimensional modeling of description. L < ₁ > is ethylene group or a propylene group in Formula (2), The photocurable composition for three-dimensional model | molding as described in any one of Claim 2 thru | or 9 characterized by the above-mentioned. The said chain extender contains the compound which has at least 2 the functional group selected from the group which consists of a hydroxyl group, an amino group, and a thiol group in 1 molecule. A photocurable composition for three-dimensional modeling according to claim 1. The (meth) acrylic compound has the following general formula (11)

(In general formula (11), A ₁ to A ₄ are each independently a structure represented by the following general formula (12), and B is a structure represented by the following general formula (13).)

(In the general formula (13), R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an optionally substituted hydrocarbon group having 1 to 10 carbon atoms, and L ₁ represents a substituent. Represents a divalent hydrocarbon group having 1 to 10 carbon atoms which may be present, and each of R _3a , R _3b , R ₄ , R ₅ , R ₆ and R ₇ in the general formula (13) Independently, it represents a divalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, Y ₁ is a divalent linking group, and a is an integer of 1 to 99. )
Containing a blocked isocyanate group represented by
The photocurable composition for three-dimensional modeling according to claim 1, further comprising a chain extender. 13. The photocuring for three-dimensional modeling according to claim 12, wherein in the general formula (12), R ₂ is a group selected from a tert-butyl group, a tert-pentyl group, and a tert-hexyl group. Sex composition. In the general formula (12), L ₁ is photocurable composition for stereolithography according to claim 12 or 13, characterized in that an ethylene or propylene group. 15. The general formula (3), wherein Y ₁ is at least one selected from the group consisting of the following formulas (C1) to (C3): A photocurable composition for three-dimensional modeling.

16. The photocurable composition for three-dimensional modeling according to any one of claims 12 to 15, wherein A ₁ to A ₄ are the same in the general formula (1). 7. The photocuring according to claim 6, wherein the chain extender contains a compound having at least two functional groups selected from the group consisting of a hydroxyl group, an amino group, and a thiol group in one molecule. Sex composition. It is a manufacturing method of a solid thing which has the process of photocuring the photocurable composition for three-dimensional modeling based on slice data, and modeling a modeling thing,
The method for producing a three-dimensional object, wherein the photocurable composition for three-dimensional modeling is the photocurable composition for three-dimensional modeling according to any one of claims 1 to 17. The step of photocuring the photocurable composition for three-dimensional modeling based on the slice data to model the modeled object,
A step of obtaining a three-dimensional object by performing a heat treatment on the three-dimensional object,
The method for producing a three-dimensional object, wherein the photocurable composition for three-dimensional modeling is the photocurable composition for three-dimensional modeling according to any one of claims 2 to 17. The following general formula (8)

(In Formula (8), R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an optionally substituted hydrocarbon group having 1 to 10 carbon atoms, and L ₁ has a substituent. Represents a divalent hydrocarbon group having 1 to 10 carbon atoms which may be present.)
A repeating structural unit represented by the following general formula (9):

(In Formula (9), R ₃ , R ₄ and R ₅ each independently represents a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and X ₁ and X ₂ are each independently Represents one of O (oxygen atom), S (sulfur atom), and NH (imino group), and a is an integer of 1 or more and 100 or less.
Resin containing the repeating structural unit represented by these, and a polyrotaxane structure.

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